Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034009/om2139sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034009/om2139Isup2.hkl |
CCDC reference: 657775
Key indicators
- Single-crystal X-ray study
- T = 153 K
- Mean (C-C) = 0.002 Å
- R factor = 0.036
- wR factor = 0.101
- Data-to-parameter ratio = 17.2
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.66 mm PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT230_ALERT_2_C Hirshfeld Test Diff for C32 - C33 .. 6.01 su PLAT322_ALERT_2_C Check Hybridisation of S1 in Main Residue . ? PLAT322_ALERT_2_C Check Hybridisation of S2 in Main Residue . ?
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
To the mixture of 1-phenyl-3-methyl-5-phenoxylpyrazole-4-formylic acid(4 mmol) and aminothiourea(4 mmol), phosphorus oxychloride(10 mL) was slowly added with stirring in ice bath. The reaction mixture was slowly heated to reflux 2 h at about 358 K, then cooled, and cold water (30 mL) added. The solution was slowly heated to reflux 6 h at about 393 K, then filtered. To neutralize the filtrate, 25% KOH was added to reach pH = 8–9. The product was isolated by filtration, washed with water, and dried at room temperature for a yield 65.2% (0.912 g), m.p. 497–498 K. Block-like single-crystal of the title compound were grown from a solution of ethanol by slow evaporation.
The H atoms attached to the parent C or N atoms were geometrically fixed, and were treated as riding atoms, whereas the methyl H atoms were refined as rigid groups, coupled with rotation of the group to best fit the electron density map. The distances were N—H = 0.88 Å, C—H = 0.95–0.98 Å, with Uiso(H) = 1.2Ueq(C or N), U(iso(methylH) = 1.5Ueq(C).
Compounds including 1,3,4-thiadiazole ring are known to possess several biological properties, such as antibacterial, antitubercular, antineoplastic activities (Thomasco et al., 2003; Foroumadi et al., 2002; Supuran & Scozzafava, 2000). Pyrazoles also have widespread biological activity, such as antisepsis, antileukosis, antitumor (Akbas et al., 2005; Daidone et al., 2004; Park et al., 2005). In an attempt to achieve new compounds with possible biological activities, we designed and synthesized 2-amino-5-(1-phenyl-3-methyl-5-phenoxylpyrazole-4-yl)-1,3,4-thiadiazole(1). The asymmetric unit has two molecules, and structures of the two molecules are nearly identical.
For related literature, see: Akbas et al. (2005); Daidone et al. (2004); Foroumadi et al. (2002); Park et al. (2005); Supuran & Scozzafava (2000); Thomasco et al. (2003).
Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3(Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C18H15N5OS | Dx = 1.363 Mg m−3 |
Mr = 349.41 | Melting point: 498 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 20.2987 (5) Å | Cell parameters from 26663 reflections |
b = 9.6934 (3) Å | θ = 3.0–27.5° |
c = 19.0726 (6) Å | µ = 0.21 mm−1 |
β = 114.846 (1)° | T = 153 K |
V = 3405.43 (17) Å3 | Block, colorless |
Z = 8 | 0.66 × 0.43 × 0.31 mm |
F(000) = 1456 |
Rigaku R-AXIS SPIDER diffractometer | 7772 independent reflections |
Radiation source: fine-focus sealed tube | 6769 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
ω scans | θmax = 27.5°, θmin = 3.0° |
Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995) | h = −24→26 |
Tmin = 0.876, Tmax = 0.939 | k = −12→12 |
32693 measured reflections | l = −24→23 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0577P)2 + 0.8824P] where P = (Fo2 + 2Fc2)/3 |
7772 reflections | (Δ/σ)max = 0.001 |
453 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
C18H15N5OS | V = 3405.43 (17) Å3 |
Mr = 349.41 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 20.2987 (5) Å | µ = 0.21 mm−1 |
b = 9.6934 (3) Å | T = 153 K |
c = 19.0726 (6) Å | 0.66 × 0.43 × 0.31 mm |
β = 114.846 (1)° |
Rigaku R-AXIS SPIDER diffractometer | 7772 independent reflections |
Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995) | 6769 reflections with I > 2σ(I) |
Tmin = 0.876, Tmax = 0.939 | Rint = 0.020 |
32693 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.24 e Å−3 |
7772 reflections | Δρmin = −0.41 e Å−3 |
453 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 | ||
S1 | 0.430303 (16) | 0.79622 (3) | 0.268570 (16) | 0.02420 (8) | |
S2 | 0.053694 (17) | 0.72302 (4) | 0.263009 (18) | 0.03485 (10) | |
O1 | 0.52710 (4) | 0.88205 (9) | 0.18168 (5) | 0.02343 (18) | |
O2 | −0.04172 (5) | 0.82952 (9) | 0.34655 (5) | 0.02735 (19) | |
N1 | 0.33984 (6) | 0.79945 (13) | 0.34137 (6) | 0.0323 (3) | |
H1A | 0.2967 | 0.7916 | 0.3416 | 0.039* | |
H1B | 0.3779 | 0.8193 | 0.3844 | 0.039* | |
N2 | 0.29285 (6) | 0.75129 (12) | 0.20940 (6) | 0.0250 (2) | |
N3 | 0.31332 (5) | 0.73761 (11) | 0.14935 (6) | 0.0236 (2) | |
N4 | 0.43532 (5) | 0.68631 (11) | 0.01202 (6) | 0.0234 (2) | |
N5 | 0.49192 (5) | 0.76583 (11) | 0.06123 (6) | 0.0225 (2) | |
N6 | 0.14095 (6) | 0.71887 (15) | 0.18704 (7) | 0.0384 (3) | |
H6A | 0.1835 | 0.7101 | 0.1857 | 0.046* | |
H6B | 0.1017 | 0.7308 | 0.1439 | 0.046* | |
N7 | 0.19232 (6) | 0.69641 (13) | 0.32166 (6) | 0.0295 (2) | |
N8 | 0.17298 (6) | 0.68692 (12) | 0.38289 (6) | 0.0285 (2) | |
N9 | 0.05654 (5) | 0.67127 (12) | 0.52749 (6) | 0.0269 (2) | |
N10 | −0.00125 (5) | 0.74338 (12) | 0.47454 (6) | 0.0249 (2) | |
C1 | 0.58095 (6) | 0.93578 (13) | 0.06074 (7) | 0.0267 (3) | |
H1C | 0.5691 | 0.9941 | 0.0938 | 0.032* | |
C2 | 0.63228 (7) | 0.97676 (15) | 0.03447 (8) | 0.0316 (3) | |
H2B | 0.6565 | 1.0627 | 0.0506 | 0.038* | |
C3 | 0.64825 (8) | 0.89297 (16) | −0.01502 (9) | 0.0380 (3) | |
H3B | 0.6829 | 0.9219 | −0.0333 | 0.046* | |
C4 | 0.61364 (9) | 0.76660 (17) | −0.03796 (10) | 0.0414 (3) | |
H4B | 0.6242 | 0.7099 | −0.0726 | 0.050* | |
C5 | 0.56374 (8) | 0.72254 (15) | −0.01070 (8) | 0.0334 (3) | |
H5A | 0.5412 | 0.6348 | −0.0251 | 0.040* | |
C6 | 0.54718 (6) | 0.80857 (13) | 0.03806 (7) | 0.0235 (2) | |
C7 | 0.32015 (7) | 0.59679 (14) | 0.00612 (7) | 0.0283 (3) | |
H7B | 0.3224 | 0.5393 | −0.0351 | 0.042* | |
H7C | 0.2798 | 0.6622 | −0.0161 | 0.042* | |
H7D | 0.3126 | 0.5380 | 0.0439 | 0.042* | |
C8 | 0.38972 (6) | 0.67421 (12) | 0.04516 (6) | 0.0218 (2) | |
C9 | 0.41636 (6) | 0.74462 (12) | 0.11713 (6) | 0.0212 (2) | |
C10 | 0.48134 (6) | 0.80017 (12) | 0.12464 (6) | 0.0209 (2) | |
C11 | 0.59244 (6) | 0.82460 (12) | 0.23525 (6) | 0.0206 (2) | |
C12 | 0.60255 (7) | 0.68515 (13) | 0.25028 (8) | 0.0289 (3) | |
H12A | 0.5653 | 0.6208 | 0.2227 | 0.035* | |
C13 | 0.66881 (8) | 0.64136 (15) | 0.30706 (8) | 0.0342 (3) | |
H13A | 0.6770 | 0.5457 | 0.3182 | 0.041* | |
C14 | 0.72283 (7) | 0.73517 (15) | 0.34745 (8) | 0.0324 (3) | |
H14A | 0.7677 | 0.7042 | 0.3864 | 0.039* | |
C15 | 0.71116 (7) | 0.87414 (15) | 0.33085 (8) | 0.0334 (3) | |
H15A | 0.7482 | 0.9389 | 0.3583 | 0.040* | |
C16 | 0.64566 (7) | 0.91945 (13) | 0.27442 (7) | 0.0288 (3) | |
H16A | 0.6376 | 1.0150 | 0.2629 | 0.035* | |
C17 | 0.38236 (6) | 0.75766 (12) | 0.17010 (6) | 0.0208 (2) | |
C18 | 0.34753 (7) | 0.78104 (12) | 0.27530 (7) | 0.0236 (2) | |
C19 | −0.08683 (7) | 0.92639 (14) | 0.46842 (8) | 0.0306 (3) | |
H19A | −0.0778 | 0.9722 | 0.4293 | 0.037* | |
C20 | −0.13382 (7) | 0.98335 (16) | 0.49647 (8) | 0.0371 (3) | |
H20A | −0.1574 | 1.0683 | 0.4760 | 0.044* | |
C21 | −0.14653 (8) | 0.9176 (2) | 0.55371 (9) | 0.0460 (4) | |
H21A | −0.1782 | 0.9578 | 0.5731 | 0.055* | |
C22 | −0.11300 (8) | 0.7928 (2) | 0.58291 (9) | 0.0484 (4) | |
H22A | −0.1219 | 0.7475 | 0.6223 | 0.058* | |
C23 | −0.06649 (7) | 0.73330 (17) | 0.55515 (8) | 0.0360 (3) | |
H23A | −0.0440 | 0.6471 | 0.5747 | 0.043* | |
C24 | −0.05322 (6) | 0.80151 (14) | 0.49835 (7) | 0.0261 (3) | |
C25 | 0.16923 (7) | 0.56799 (15) | 0.53478 (8) | 0.0318 (3) | |
H25A | 0.1701 | 0.5290 | 0.5826 | 0.048* | |
H25B | 0.2101 | 0.6317 | 0.5473 | 0.048* | |
H25C | 0.1731 | 0.4934 | 0.5020 | 0.048* | |
C26 | 0.09973 (6) | 0.64382 (13) | 0.49282 (7) | 0.0248 (2) | |
C27 | 0.07052 (6) | 0.69711 (13) | 0.41642 (7) | 0.0238 (2) | |
C28 | 0.00615 (6) | 0.75820 (13) | 0.40755 (7) | 0.0238 (2) | |
C29 | −0.10629 (6) | 0.76360 (14) | 0.29741 (7) | 0.0249 (2) | |
C30 | −0.11821 (7) | 0.62435 (15) | 0.29970 (9) | 0.0356 (3) | |
H30A | −0.0826 | 0.5666 | 0.3365 | 0.043* | |
C31 | −0.18401 (9) | 0.57004 (19) | 0.24642 (10) | 0.0491 (4) | |
H31A | −0.1932 | 0.4741 | 0.2471 | 0.059* | |
C32 | −0.23534 (8) | 0.6529 (2) | 0.19326 (9) | 0.0497 (4) | |
H32A | −0.2797 | 0.6145 | 0.1571 | 0.060* | |
C33 | −0.22249 (8) | 0.7914 (2) | 0.19243 (9) | 0.0504 (5) | |
H33A | −0.2583 | 0.8489 | 0.1557 | 0.061* | |
C34 | −0.15764 (8) | 0.84882 (17) | 0.24470 (8) | 0.0378 (3) | |
H34A | −0.1489 | 0.9450 | 0.2441 | 0.045* | |
C35 | 0.10357 (6) | 0.69930 (13) | 0.36219 (7) | 0.0242 (2) | |
C36 | 0.13585 (7) | 0.71394 (14) | 0.25529 (7) | 0.0280 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.02217 (15) | 0.03248 (17) | 0.01766 (15) | −0.00192 (11) | 0.00807 (12) | −0.00262 (11) |
S2 | 0.02132 (15) | 0.0625 (2) | 0.01953 (16) | 0.00335 (14) | 0.00740 (13) | 0.00420 (14) |
O1 | 0.0210 (4) | 0.0248 (4) | 0.0194 (4) | 0.0012 (3) | 0.0036 (3) | −0.0025 (3) |
O2 | 0.0248 (4) | 0.0307 (5) | 0.0223 (4) | 0.0007 (3) | 0.0059 (4) | 0.0038 (3) |
N1 | 0.0266 (5) | 0.0531 (7) | 0.0187 (5) | 0.0006 (5) | 0.0112 (4) | −0.0021 (5) |
N2 | 0.0228 (5) | 0.0347 (6) | 0.0186 (5) | 0.0040 (4) | 0.0098 (4) | 0.0025 (4) |
N3 | 0.0222 (5) | 0.0309 (5) | 0.0181 (5) | 0.0034 (4) | 0.0090 (4) | 0.0021 (4) |
N4 | 0.0203 (5) | 0.0300 (5) | 0.0181 (5) | −0.0027 (4) | 0.0064 (4) | −0.0027 (4) |
N5 | 0.0190 (5) | 0.0291 (5) | 0.0184 (5) | −0.0018 (4) | 0.0070 (4) | −0.0017 (4) |
N6 | 0.0264 (6) | 0.0677 (9) | 0.0219 (6) | 0.0031 (5) | 0.0110 (5) | 0.0056 (5) |
N7 | 0.0234 (5) | 0.0446 (7) | 0.0214 (5) | 0.0003 (4) | 0.0102 (4) | 0.0019 (4) |
N8 | 0.0228 (5) | 0.0421 (6) | 0.0203 (5) | −0.0014 (4) | 0.0088 (4) | 0.0003 (4) |
N9 | 0.0213 (5) | 0.0372 (6) | 0.0192 (5) | 0.0019 (4) | 0.0058 (4) | 0.0016 (4) |
N10 | 0.0194 (5) | 0.0349 (6) | 0.0189 (5) | 0.0014 (4) | 0.0065 (4) | 0.0007 (4) |
C1 | 0.0248 (6) | 0.0296 (6) | 0.0249 (6) | 0.0019 (5) | 0.0094 (5) | 0.0029 (5) |
C2 | 0.0276 (6) | 0.0338 (7) | 0.0319 (7) | −0.0019 (5) | 0.0111 (5) | 0.0075 (5) |
C3 | 0.0332 (7) | 0.0480 (9) | 0.0409 (8) | −0.0021 (6) | 0.0235 (6) | 0.0069 (6) |
C4 | 0.0443 (8) | 0.0474 (9) | 0.0465 (9) | −0.0021 (7) | 0.0328 (8) | −0.0055 (7) |
C5 | 0.0348 (7) | 0.0354 (7) | 0.0379 (7) | −0.0032 (5) | 0.0230 (6) | −0.0048 (6) |
C6 | 0.0190 (5) | 0.0310 (6) | 0.0209 (6) | 0.0022 (4) | 0.0088 (5) | 0.0045 (5) |
C7 | 0.0250 (6) | 0.0360 (7) | 0.0230 (6) | −0.0064 (5) | 0.0094 (5) | −0.0040 (5) |
C8 | 0.0215 (5) | 0.0261 (6) | 0.0166 (5) | 0.0001 (4) | 0.0066 (4) | 0.0007 (4) |
C9 | 0.0213 (5) | 0.0251 (6) | 0.0165 (5) | 0.0014 (4) | 0.0071 (4) | 0.0016 (4) |
C10 | 0.0205 (5) | 0.0236 (5) | 0.0167 (5) | 0.0020 (4) | 0.0059 (4) | 0.0006 (4) |
C11 | 0.0196 (5) | 0.0254 (6) | 0.0165 (5) | 0.0011 (4) | 0.0073 (4) | −0.0005 (4) |
C12 | 0.0289 (6) | 0.0244 (6) | 0.0284 (6) | −0.0028 (5) | 0.0070 (5) | 0.0001 (5) |
C13 | 0.0364 (7) | 0.0276 (6) | 0.0333 (7) | 0.0070 (5) | 0.0096 (6) | 0.0044 (5) |
C14 | 0.0245 (6) | 0.0436 (8) | 0.0243 (6) | 0.0088 (5) | 0.0055 (5) | 0.0011 (5) |
C15 | 0.0241 (6) | 0.0394 (8) | 0.0292 (7) | −0.0045 (5) | 0.0038 (5) | −0.0072 (6) |
C16 | 0.0283 (6) | 0.0247 (6) | 0.0285 (6) | −0.0015 (5) | 0.0070 (5) | −0.0028 (5) |
C17 | 0.0220 (5) | 0.0232 (5) | 0.0161 (5) | 0.0021 (4) | 0.0070 (4) | 0.0017 (4) |
C18 | 0.0246 (6) | 0.0260 (6) | 0.0214 (6) | 0.0039 (4) | 0.0110 (5) | 0.0031 (4) |
C19 | 0.0246 (6) | 0.0352 (7) | 0.0295 (7) | −0.0037 (5) | 0.0089 (5) | −0.0052 (5) |
C20 | 0.0254 (6) | 0.0434 (8) | 0.0360 (8) | 0.0026 (6) | 0.0066 (6) | −0.0123 (6) |
C21 | 0.0279 (7) | 0.0770 (12) | 0.0327 (8) | 0.0111 (7) | 0.0124 (6) | −0.0084 (7) |
C22 | 0.0328 (7) | 0.0861 (13) | 0.0318 (8) | 0.0097 (8) | 0.0191 (7) | 0.0092 (8) |
C23 | 0.0266 (6) | 0.0548 (9) | 0.0276 (7) | 0.0049 (6) | 0.0123 (6) | 0.0064 (6) |
C24 | 0.0180 (5) | 0.0374 (7) | 0.0216 (6) | −0.0028 (5) | 0.0070 (5) | −0.0061 (5) |
C25 | 0.0244 (6) | 0.0430 (8) | 0.0245 (6) | 0.0050 (5) | 0.0068 (5) | 0.0028 (5) |
C26 | 0.0212 (5) | 0.0312 (6) | 0.0196 (5) | −0.0021 (5) | 0.0063 (5) | −0.0018 (5) |
C27 | 0.0213 (5) | 0.0296 (6) | 0.0189 (6) | −0.0020 (4) | 0.0070 (5) | −0.0017 (4) |
C28 | 0.0211 (5) | 0.0293 (6) | 0.0189 (6) | −0.0021 (4) | 0.0063 (5) | −0.0004 (4) |
C29 | 0.0214 (5) | 0.0349 (7) | 0.0181 (5) | 0.0048 (5) | 0.0081 (5) | −0.0011 (5) |
C30 | 0.0286 (6) | 0.0337 (7) | 0.0373 (7) | 0.0028 (5) | 0.0069 (6) | −0.0039 (6) |
C31 | 0.0389 (8) | 0.0492 (10) | 0.0530 (10) | −0.0079 (7) | 0.0133 (8) | −0.0193 (8) |
C32 | 0.0275 (7) | 0.0824 (13) | 0.0322 (8) | −0.0039 (8) | 0.0056 (6) | −0.0215 (8) |
C33 | 0.0302 (7) | 0.0860 (14) | 0.0261 (7) | 0.0194 (8) | 0.0031 (6) | 0.0071 (8) |
C34 | 0.0354 (7) | 0.0438 (8) | 0.0304 (7) | 0.0124 (6) | 0.0102 (6) | 0.0085 (6) |
C35 | 0.0228 (5) | 0.0294 (6) | 0.0184 (5) | −0.0013 (4) | 0.0066 (5) | −0.0016 (4) |
C36 | 0.0244 (6) | 0.0373 (7) | 0.0230 (6) | 0.0000 (5) | 0.0106 (5) | 0.0010 (5) |
S1—C18 | 1.7442 (12) | C8—C9 | 1.4207 (16) |
S1—C17 | 1.7545 (12) | C9—C10 | 1.3755 (16) |
S2—C36 | 1.7370 (13) | C9—C17 | 1.4488 (15) |
S2—C35 | 1.7454 (12) | C11—C16 | 1.3757 (17) |
O1—C10 | 1.3517 (14) | C11—C12 | 1.3791 (17) |
O1—C11 | 1.4050 (14) | C12—C13 | 1.3922 (18) |
O2—C28 | 1.3512 (15) | C12—H12A | 0.9500 |
O2—C29 | 1.4043 (15) | C13—C14 | 1.383 (2) |
N1—C18 | 1.3452 (15) | C13—H13A | 0.9500 |
N1—H1A | 0.8800 | C14—C15 | 1.381 (2) |
N1—H1B | 0.8800 | C14—H14A | 0.9500 |
N2—C18 | 1.3124 (16) | C15—C16 | 1.3844 (18) |
N2—N3 | 1.3791 (13) | C15—H15A | 0.9500 |
N3—C17 | 1.3007 (15) | C16—H16A | 0.9500 |
N4—C8 | 1.3272 (15) | C19—C20 | 1.3892 (18) |
N4—N5 | 1.3743 (14) | C19—C24 | 1.3891 (19) |
N5—C10 | 1.3556 (15) | C19—H19A | 0.9500 |
N5—C6 | 1.4288 (15) | C20—C21 | 1.379 (2) |
N6—C36 | 1.3493 (17) | C20—H20A | 0.9500 |
N6—H6A | 0.8800 | C21—C22 | 1.385 (3) |
N6—H6B | 0.8800 | C21—H21A | 0.9500 |
N7—C36 | 1.3136 (17) | C22—C23 | 1.387 (2) |
N7—N8 | 1.3826 (14) | C22—H22A | 0.9500 |
N8—C35 | 1.2991 (16) | C23—C24 | 1.3888 (19) |
N9—C26 | 1.3279 (16) | C23—H23A | 0.9500 |
N9—N10 | 1.3744 (14) | C25—C26 | 1.4908 (17) |
N10—C28 | 1.3555 (15) | C25—H25A | 0.9800 |
N10—C24 | 1.4279 (15) | C25—H25B | 0.9800 |
C1—C6 | 1.3887 (18) | C25—H25C | 0.9800 |
C1—C2 | 1.3904 (17) | C26—C27 | 1.4198 (17) |
C1—H1C | 0.9500 | C27—C28 | 1.3787 (17) |
C2—C3 | 1.383 (2) | C27—C35 | 1.4503 (16) |
C2—H2B | 0.9500 | C29—C30 | 1.375 (2) |
C3—C4 | 1.388 (2) | C29—C34 | 1.3781 (18) |
C3—H3B | 0.9500 | C30—C31 | 1.398 (2) |
C4—C5 | 1.3859 (19) | C30—H30A | 0.9500 |
C4—H4B | 0.9500 | C31—C32 | 1.368 (3) |
C5—C6 | 1.3915 (18) | C31—H31A | 0.9500 |
C5—H5A | 0.9500 | C32—C33 | 1.369 (3) |
C7—C8 | 1.4927 (16) | C32—H32A | 0.9500 |
C7—H7B | 0.9800 | C33—C34 | 1.391 (2) |
C7—H7C | 0.9800 | C33—H33A | 0.9500 |
C7—H7D | 0.9800 | C34—H34A | 0.9500 |
C18—S1—C17 | 86.71 (5) | C14—C15—H15A | 119.9 |
C36—S2—C35 | 86.84 (6) | C16—C15—H15A | 119.9 |
C10—O1—C11 | 118.17 (9) | C11—C16—C15 | 119.26 (12) |
C28—O2—C29 | 118.28 (10) | C11—C16—H16A | 120.4 |
C18—N1—H1A | 120.0 | C15—C16—H16A | 120.4 |
C18—N1—H1B | 120.0 | N3—C17—C9 | 122.87 (10) |
H1A—N1—H1B | 120.0 | N3—C17—S1 | 113.56 (8) |
C18—N2—N3 | 112.82 (10) | C9—C17—S1 | 123.54 (9) |
C17—N3—N2 | 113.26 (10) | N2—C18—N1 | 122.82 (11) |
C8—N4—N5 | 105.94 (9) | N2—C18—S1 | 113.65 (9) |
C10—N5—N4 | 110.28 (9) | N1—C18—S1 | 123.52 (10) |
C10—N5—C6 | 130.08 (10) | C20—C19—C24 | 119.10 (13) |
N4—N5—C6 | 119.42 (9) | C20—C19—H19A | 120.4 |
C36—N6—H6A | 120.0 | C24—C19—H19A | 120.4 |
C36—N6—H6B | 120.0 | C21—C20—C19 | 120.55 (14) |
H6A—N6—H6B | 120.0 | C21—C20—H20A | 119.7 |
C36—N7—N8 | 112.34 (10) | C19—C20—H20A | 119.7 |
C35—N8—N7 | 113.19 (10) | C20—C21—C22 | 119.89 (13) |
C26—N9—N10 | 105.92 (10) | C20—C21—H21A | 120.1 |
C28—N10—N9 | 110.37 (10) | C22—C21—H21A | 120.1 |
C28—N10—C24 | 130.33 (11) | C21—C22—C23 | 120.51 (15) |
N9—N10—C24 | 118.92 (10) | C21—C22—H22A | 119.7 |
C6—C1—C2 | 119.22 (12) | C23—C22—H22A | 119.7 |
C6—C1—H1C | 120.4 | C22—C23—C24 | 119.09 (15) |
C2—C1—H1C | 120.4 | C22—C23—H23A | 120.5 |
C3—C2—C1 | 120.27 (13) | C24—C23—H23A | 120.5 |
C3—C2—H2B | 119.9 | C23—C24—C19 | 120.84 (12) |
C1—C2—H2B | 119.9 | C23—C24—N10 | 118.13 (12) |
C2—C3—C4 | 120.04 (12) | C19—C24—N10 | 120.95 (11) |
C2—C3—H3B | 120.0 | C26—C25—H25A | 109.5 |
C4—C3—H3B | 120.0 | C26—C25—H25B | 109.5 |
C5—C4—C3 | 120.43 (14) | H25A—C25—H25B | 109.5 |
C5—C4—H4B | 119.8 | C26—C25—H25C | 109.5 |
C3—C4—H4B | 119.8 | H25A—C25—H25C | 109.5 |
C4—C5—C6 | 119.08 (13) | H25B—C25—H25C | 109.5 |
C4—C5—H5A | 120.5 | N9—C26—C27 | 111.09 (11) |
C6—C5—H5A | 120.5 | N9—C26—C25 | 120.35 (11) |
C1—C6—C5 | 120.93 (11) | C27—C26—C25 | 128.55 (11) |
C1—C6—N5 | 120.67 (11) | C28—C27—C26 | 104.34 (10) |
C5—C6—N5 | 118.33 (11) | C28—C27—C35 | 127.21 (11) |
C8—C7—H7B | 109.5 | C26—C27—C35 | 128.21 (11) |
C8—C7—H7C | 109.5 | O2—C28—N10 | 122.78 (11) |
H7B—C7—H7C | 109.5 | O2—C28—C27 | 128.84 (11) |
C8—C7—H7D | 109.5 | N10—C28—C27 | 108.27 (11) |
H7B—C7—H7D | 109.5 | C30—C29—C34 | 121.48 (13) |
H7C—C7—H7D | 109.5 | C30—C29—O2 | 123.56 (11) |
N4—C8—C9 | 111.05 (10) | C34—C29—O2 | 114.95 (12) |
N4—C8—C7 | 120.65 (10) | C29—C30—C31 | 118.28 (14) |
C9—C8—C7 | 128.29 (10) | C29—C30—H30A | 120.9 |
C10—C9—C8 | 104.34 (10) | C31—C30—H30A | 120.9 |
C10—C9—C17 | 127.61 (11) | C32—C31—C30 | 121.03 (17) |
C8—C9—C17 | 128.04 (11) | C32—C31—H31A | 119.5 |
O1—C10—N5 | 123.32 (10) | C30—C31—H31A | 119.5 |
O1—C10—C9 | 128.20 (10) | C31—C32—C33 | 119.66 (15) |
N5—C10—C9 | 108.38 (10) | C31—C32—H32A | 120.2 |
C16—C11—C12 | 121.86 (11) | C33—C32—H32A | 120.2 |
C16—C11—O1 | 114.58 (10) | C32—C33—C34 | 120.81 (15) |
C12—C11—O1 | 123.52 (11) | C32—C33—H33A | 119.6 |
C11—C12—C13 | 118.12 (12) | C34—C33—H33A | 119.6 |
C11—C12—H12A | 120.9 | C29—C34—C33 | 118.74 (15) |
C13—C12—H12A | 120.9 | C29—C34—H34A | 120.6 |
C14—C13—C12 | 120.90 (13) | C33—C34—H34A | 120.6 |
C14—C13—H13A | 119.6 | N8—C35—C27 | 123.33 (11) |
C12—C13—H13A | 119.6 | N8—C35—S2 | 113.75 (9) |
C15—C14—C13 | 119.61 (12) | C27—C35—S2 | 122.91 (9) |
C15—C14—H14A | 120.2 | N7—C36—N6 | 123.00 (12) |
C13—C14—H14A | 120.2 | N7—C36—S2 | 113.89 (9) |
C14—C15—C16 | 120.25 (12) | N6—C36—S2 | 123.06 (10) |
C18—N2—N3—C17 | −0.36 (15) | N3—N2—C18—S1 | 0.46 (14) |
C8—N4—N5—C10 | 0.95 (13) | C17—S1—C18—N2 | −0.33 (10) |
C8—N4—N5—C6 | −174.12 (10) | C17—S1—C18—N1 | −179.62 (12) |
C36—N7—N8—C35 | −0.94 (17) | C24—C19—C20—C21 | 0.5 (2) |
C26—N9—N10—C28 | 0.83 (14) | C19—C20—C21—C22 | −0.9 (2) |
C26—N9—N10—C24 | −172.83 (11) | C20—C21—C22—C23 | 0.2 (3) |
C6—C1—C2—C3 | 1.42 (19) | C21—C22—C23—C24 | 0.8 (2) |
C1—C2—C3—C4 | −0.8 (2) | C22—C23—C24—C19 | −1.1 (2) |
C2—C3—C4—C5 | −0.9 (2) | C22—C23—C24—N10 | 175.63 (13) |
C3—C4—C5—C6 | 2.0 (2) | C20—C19—C24—C23 | 0.46 (19) |
C2—C1—C6—C5 | −0.36 (19) | C20—C19—C24—N10 | −176.23 (11) |
C2—C1—C6—N5 | −177.25 (11) | C28—N10—C24—C23 | 156.26 (13) |
C4—C5—C6—C1 | −1.3 (2) | N9—N10—C24—C23 | −31.54 (17) |
C4—C5—C6—N5 | 175.65 (13) | C28—N10—C24—C19 | −27.0 (2) |
C10—N5—C6—C1 | −27.86 (19) | N9—N10—C24—C19 | 145.24 (12) |
N4—N5—C6—C1 | 146.09 (11) | N10—N9—C26—C27 | −0.30 (14) |
C10—N5—C6—C5 | 155.17 (13) | N10—N9—C26—C25 | 178.83 (11) |
N4—N5—C6—C5 | −30.88 (17) | N9—C26—C27—C28 | −0.31 (14) |
N5—N4—C8—C9 | −0.65 (13) | C25—C26—C27—C28 | −179.36 (13) |
N5—N4—C8—C7 | 178.21 (11) | N9—C26—C27—C35 | 174.30 (12) |
N4—C8—C9—C10 | 0.12 (14) | C25—C26—C27—C35 | −4.7 (2) |
C7—C8—C9—C10 | −178.63 (12) | C29—O2—C28—N10 | −80.86 (15) |
N4—C8—C9—C17 | 179.00 (11) | C29—O2—C28—C27 | 103.48 (15) |
C7—C8—C9—C17 | 0.3 (2) | N9—N10—C28—O2 | −177.49 (11) |
C11—O1—C10—N5 | −77.24 (14) | C24—N10—C28—O2 | −4.8 (2) |
C11—O1—C10—C9 | 106.74 (14) | N9—N10—C28—C27 | −1.05 (14) |
N4—N5—C10—O1 | −177.60 (10) | C24—N10—C28—C27 | 171.67 (12) |
C6—N5—C10—O1 | −3.22 (19) | C26—C27—C28—O2 | 176.96 (12) |
N4—N5—C10—C9 | −0.90 (13) | C35—C27—C28—O2 | 2.3 (2) |
C6—N5—C10—C9 | 173.49 (11) | C26—C27—C28—N10 | 0.81 (14) |
C8—C9—C10—O1 | 176.97 (11) | C35—C27—C28—N10 | −173.88 (12) |
C17—C9—C10—O1 | −1.9 (2) | C28—O2—C29—C30 | −11.62 (17) |
C8—C9—C10—N5 | 0.47 (13) | C28—O2—C29—C34 | 169.42 (11) |
C17—C9—C10—N5 | −178.42 (11) | C34—C29—C30—C31 | 0.5 (2) |
C10—O1—C11—C16 | 159.41 (10) | O2—C29—C30—C31 | −178.34 (13) |
C10—O1—C11—C12 | −22.92 (16) | C29—C30—C31—C32 | 0.0 (2) |
C16—C11—C12—C13 | 0.19 (19) | C30—C31—C32—C33 | −0.5 (2) |
O1—C11—C12—C13 | −177.32 (11) | C31—C32—C33—C34 | 0.4 (2) |
C11—C12—C13—C14 | 0.3 (2) | C30—C29—C34—C33 | −0.6 (2) |
C12—C13—C14—C15 | −0.5 (2) | O2—C29—C34—C33 | 178.33 (12) |
C13—C14—C15—C16 | 0.3 (2) | C32—C33—C34—C29 | 0.2 (2) |
C12—C11—C16—C15 | −0.36 (19) | N7—N8—C35—C27 | −178.05 (11) |
O1—C11—C16—C15 | 177.35 (11) | N7—N8—C35—S2 | 0.50 (15) |
C14—C15—C16—C11 | 0.1 (2) | C28—C27—C35—N8 | 153.50 (13) |
N2—N3—C17—C9 | 178.14 (11) | C26—C27—C35—N8 | −19.9 (2) |
N2—N3—C17—S1 | 0.10 (13) | C28—C27—C35—S2 | −24.92 (18) |
C10—C9—C17—N3 | 159.30 (12) | C26—C27—C35—S2 | 161.64 (11) |
C8—C9—C17—N3 | −19.3 (2) | C36—S2—C35—N8 | 0.03 (11) |
C10—C9—C17—S1 | −22.85 (18) | C36—S2—C35—C27 | 178.59 (11) |
C8—C9—C17—S1 | 158.51 (10) | N8—N7—C36—N6 | −176.50 (13) |
C18—S1—C17—N3 | 0.12 (10) | N8—N7—C36—S2 | 0.97 (15) |
C18—S1—C17—C9 | −177.90 (11) | C35—S2—C36—N7 | −0.58 (11) |
N3—N2—C18—N1 | 179.75 (11) | C35—S2—C36—N6 | 176.89 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N7 | 0.88 | 2.19 | 3.0266 (16) | 158 |
N1—H1B···N4i | 0.88 | 2.21 | 3.0113 (15) | 150 |
N6—H6A···N2 | 0.88 | 2.11 | 2.9467 (15) | 159 |
N6—H6B···N9ii | 0.88 | 2.23 | 2.9915 (16) | 145 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C18H15N5OS |
Mr | 349.41 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 153 |
a, b, c (Å) | 20.2987 (5), 9.6934 (3), 19.0726 (6) |
β (°) | 114.846 (1) |
V (Å3) | 3405.43 (17) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.21 |
Crystal size (mm) | 0.66 × 0.43 × 0.31 |
Data collection | |
Diffractometer | Rigaku R-AXIS SPIDER |
Absorption correction | Empirical (using intensity measurements) (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.876, 0.939 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32693, 7772, 6769 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.101, 1.05 |
No. of reflections | 7772 |
No. of parameters | 453 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.41 |
Computer programs: RAPID-AUTO (Rigaku, 2004), RAPID-AUTO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3(Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N7 | 0.88 | 2.19 | 3.0266 (16) | 157.8 |
N1—H1B···N4i | 0.88 | 2.21 | 3.0113 (15) | 150.4 |
N6—H6A···N2 | 0.88 | 2.11 | 2.9467 (15) | 159.1 |
N6—H6B···N9ii | 0.88 | 2.23 | 2.9915 (16) | 145.0 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+3/2, z−1/2. |
Compounds including 1,3,4-thiadiazole ring are known to possess several biological properties, such as antibacterial, antitubercular, antineoplastic activities (Thomasco et al., 2003; Foroumadi et al., 2002; Supuran & Scozzafava, 2000). Pyrazoles also have widespread biological activity, such as antisepsis, antileukosis, antitumor (Akbas et al., 2005; Daidone et al., 2004; Park et al., 2005). In an attempt to achieve new compounds with possible biological activities, we designed and synthesized 2-amino-5-(1-phenyl-3-methyl-5-phenoxylpyrazole-4-yl)-1,3,4-thiadiazole(1). The asymmetric unit has two molecules, and structures of the two molecules are nearly identical.