

Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807024701/dn2175sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536807024701/dn2175Isup2.hkl |
CCDC reference: 651492
3-thiophen-2-yl-methyl-4-aryliden amino-4,5-dihydro-1H-1,2,4-triazole-5-one (0.01 mol)was refluxed with an equivalent amount of natrium in absolute ethanol for 1 h. Then, ethyl bromoacetophenon (0.01 mol) was added and refluxed for an additional 5 h. The precipitate was filtered off, washed with H2O and recrystallized from ethyl alcohol (yield: 72.47%) to give compound 1. m.p.421–422 °K.
IR (KBr) (v, cm-1) 1698 (acetophenon-C=O), 1717 (triazole-C=O), 1584 (–C=N); 1H NMR (DMSO-d6) δ (p.p.m.) 4.27 (s, thiophen-CH2), 5.44 (s, –NCH2), 6.95–7.06 (m, 2H, arH), 7.40–7.73 (m, 4H, arH), 7.81–8.15 (m, 4H, arH), 10.12 (s, –N=CH); 13C NMR (DMSO-d6) δ (p.p.m.) 25.28 (thiophen-CH2), 51.80 (–NCH2), thiophen C:[125.42 (CH), 126.74 (CH), 126.86 (CH), 135.11(C)], ar C: [128.06 (CH), 129.56 (C), 135.11 (C), 136.72(C)], benzene C: [128.20 (CH), 128.83 (CH), 133.93 (C), 134.07 (CH)], 149.89 (triazole-C-5), 144.76 (triazole-C-3), 147.95 (–N=CH), 192.56 (acetophenon-C=O).
The crystal was poor quality. All H atoms were positioned geometrically and treated as riding on their parent atoms, with C—H = 0.93 (aromatic) and 0.97 Å (methylene) and with Uiso(H) = 1.2Ueq(C).
1,2,4 triazole and 1,2,4 triazole-5-one derivatives have pharmacological properties as antimicrobial (Holla et al., 1998; Ersan et al., 1998; İkizler et al., 1999), anti imflammatory, analgesic, antitumorial, antihypertensive, antiviral activities, coccidiostatic (Tozkoparan et al., 2000; Turan-Zitouni et al.; 1999, Holla et al., 2002). It was reported that compounds having triazole moieties such as Vorozole, Anastrozole and Letrozole appear to be very effective aromatase inhibitors very useful for preventing breast cancer (Goss et al., 2004, Santen 2003, Clemons et al., 2004). Spectroscopic and crystal structure data of some di-1,2,4-triazole-5-ones have been reported previously (Sancak et al., 2005).
The compound was prepared and first identifed by NMR spectroscopy. In order to confirm the geometry, its X-ray structure determination was carried out. Compound (I) contains four planar rings (Fig. 1), namely two benzene rings [C22—C27 (A) and C33—C38 (B)], a triazole ring (C) and a thiophene ring (D). Deviations from the ideal bond-angle geometry around the Nsp2 atoms of the single bond are observed. The N21—N2—C1 and N1—N3—C31 bond angles are 120.6 (3)° and 120.8 (3)°, respectively, too close to the ideal geometry (120°); however, the N21—N2—C2, C2—N3—C31 and N1—N3—C2 angles [130 (3)°, 124.5 (3)° and 114.1 (3)°, respectively] are distorted. In the triazole ring atom C2 deviate significantly from planarity. We can conclude, that the reason for these two deviation is intramolecular and intermolecular hydrogen bonds with the O21 atom.
The N21═C21 bond length [1.269 (4) Å] agree with values reported in the literature [1.261 (4) Å in the 4-amino-3-methtl-1,2,4-triazole- 5-thione derivative of p-nitrobenzaldehyde (Liu et al., 1999), 1.267 (2) Å in 4-(4-hydroxybenzylidenamino)-4H-1,2,4-triazole hemihydrate (Zhu et al., 2000) and 1.271 (3) Å in the 1-acetyl-4- (p-chlorobenzylideneamino)-3-methyl-4,5-dihydro-1H-1,2,4-triazol-5-one (Çoruh et al., 2003)]. The presence of a substituent on N3 causes a lengthening of the N—N bond length [N1—N3= 1.385 (4) Å] with respect to the corresponding bonds in 5-(2-chlorophenyl)-4-phenyl-3,4-dihydro-2H-1,2,4-triazole-3-thione [N—N= 1.374 (2) Å; Puviarasan et al., 1999] and in 4-methyl-1,2,4- triazole and 1-methyltetrazole [N—N= 1.344 (2) Å; Palmer & Parsons, 1996]. The S—C bond lengths [S11—C12= 1.692 (6) Å and S11—C15= 1.685 (5) Å] agree with value reported in the literature (Vrábel et al., 2005; Yılmaz et al., 2006)].
The thiophene ring is disordered over two positions, corresponding to rotation of approximately 180° about the single C11—C12 bond, with a major-minor ratio of about 78.5:21.5. Such flip-type disorder is rather common in thiophene rings. Weak C—H···O hydrogen bonds may help in stabilizing the crystal structure.
For related literature, see: Clemons et al. (2004); Ersan et al. (1998); Goss & Strasser-Weippl (2004); Holla et al. (1998, 2002); Liu et al. (1999); Palmer & Parsons (1996); Puviarasan et al. (1999); Sancak et al. (2005); Santen (2003); Tozkoparan et al. (2000); Turan-Zitouni, Kaplancikli, Erol & Kilic (1999); Vrábel et al. (2005); Yılmaz, Arslan, Kazak, Sancak & Er (2006); Zhu et al. (2000); Çoruh et al. (2003); İkizler et al. (1999).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![]() | Fig. 1. An ORTEP drawing of (I), with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
C22H16Cl2N4O2S | F(000) = 1936 |
Mr = 471.35 | Dx = 1.461 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 1671 reflections |
a = 10.9045 (13) Å | θ = 1.9–28.0° |
b = 18.509 (2) Å | µ = 0.43 mm−1 |
c = 21.228 (3) Å | T = 293 K |
V = 4284.4 (9) Å3 | Prism, colourless |
Z = 8 | 0.30 × 0.25 × 0.20 mm |
Bruker SMART CCD area-detector diffractometer | 1671 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.103 |
Graphite monochromator | θmax = 28.0°, θmin = 1.9° |
φ and ω scans | h = −14→14 |
20905 measured reflections | k = −24→18 |
5052 independent reflections | l = −27→28 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.131 | H-atom parameters constrained |
S = 0.84 | w = 1/[σ2(Fo2) + (0.0469P)2] where P = (Fo2 + 2Fc2)/3 |
5052 reflections | (Δ/σ)max < 0.001 |
301 parameters | Δρmax = 0.45 e Å−3 |
148 restraints | Δρmin = −0.25 e Å−3 |
C22H16Cl2N4O2S | V = 4284.4 (9) Å3 |
Mr = 471.35 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 10.9045 (13) Å | µ = 0.43 mm−1 |
b = 18.509 (2) Å | T = 293 K |
c = 21.228 (3) Å | 0.30 × 0.25 × 0.20 mm |
Bruker SMART CCD area-detector diffractometer | 1671 reflections with I > 2σ(I) |
20905 measured reflections | Rint = 0.103 |
5052 independent reflections |
R[F2 > 2σ(F2)] = 0.049 | 148 restraints |
wR(F2) = 0.131 | H-atom parameters constrained |
S = 0.84 | Δρmax = 0.45 e Å−3 |
5052 reflections | Δρmin = −0.25 e Å−3 |
301 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 | Occ. (<1) | |
Cl21 | 1.32634 (11) | 0.05797 (7) | 0.56626 (5) | 0.0926 (4) | |
Cl22 | 1.36468 (11) | −0.14685 (6) | 0.39064 (6) | 0.1026 (5) | |
O21 | 1.0206 (2) | 0.19915 (13) | 0.60310 (11) | 0.0607 (7) | |
N21 | 0.9952 (3) | 0.12711 (16) | 0.47299 (13) | 0.0509 (8) | |
N2 | 0.9344 (2) | 0.18406 (16) | 0.50114 (13) | 0.0480 (7) | |
N1 | 0.7847 (3) | 0.26329 (17) | 0.50817 (15) | 0.0605 (9) | |
N3 | 0.8565 (3) | 0.26362 (16) | 0.56198 (14) | 0.0570 (8) | |
C21 | 1.0907 (3) | 0.1034 (2) | 0.50017 (17) | 0.0525 (10) | |
H21 | 1.1181 | 0.1249 | 0.5371 | 0.063* | |
C22 | 1.1579 (3) | 0.04203 (19) | 0.47348 (17) | 0.0465 (9) | |
C2 | 0.9483 (3) | 0.2137 (2) | 0.56163 (18) | 0.0497 (9) | |
C26 | 1.3275 (4) | −0.0427 (2) | 0.4762 (2) | 0.0662 (11) | |
H26 | 1.3978 | −0.0599 | 0.4960 | 0.079* | |
C27 | 1.2647 (3) | 0.0163 (2) | 0.50036 (17) | 0.0547 (10) | |
C33 | 0.8744 (3) | 0.4183 (2) | 0.68112 (18) | 0.0543 (10) | |
C1 | 0.8337 (3) | 0.2147 (2) | 0.47287 (17) | 0.0533 (10) | |
C31 | 0.8221 (3) | 0.30610 (19) | 0.61592 (15) | 0.0547 (10) | |
H31A | 0.8254 | 0.2758 | 0.6532 | 0.066* | |
H31B | 0.7380 | 0.3221 | 0.6107 | 0.066* | |
C32 | 0.9029 (3) | 0.3716 (2) | 0.62635 (18) | 0.0531 (10) | |
O31 | 0.9870 (3) | 0.38367 (15) | 0.59117 (14) | 0.0891 (10) | |
C11 | 0.7843 (3) | 0.1924 (2) | 0.41043 (16) | 0.0578 (9) | |
H11A | 0.6975 | 0.2038 | 0.4091 | 0.069* | |
H11B | 0.7922 | 0.1404 | 0.4066 | 0.069* | |
C12 | 0.8453 (5) | 0.2270 (3) | 0.3550 (2) | 0.0571 (9) | 0.785 (3) |
S11 | 0.98134 (13) | 0.19883 (9) | 0.32561 (8) | 0.0713 (6) | 0.785 (3) |
C13 | 0.7886 (6) | 0.2802 (4) | 0.3212 (3) | 0.0666 (12) | 0.785 (3) |
H13 | 0.7121 | 0.3004 | 0.3294 | 0.080* | 0.785 (3) |
C14 | 0.8751 (5) | 0.3000 (3) | 0.2677 (3) | 0.0716 (11) | 0.785 (3) |
H14 | 0.8590 | 0.3364 | 0.2387 | 0.086* | 0.785 (3) |
C15 | 0.9759 (5) | 0.2598 (3) | 0.2667 (3) | 0.0725 (12) | 0.785 (3) |
H15 | 1.0372 | 0.2647 | 0.2366 | 0.087* | 0.785 (3) |
C12' | 0.8527 (12) | 0.2212 (7) | 0.3532 (3) | 0.0616 (14)* | 0.215 (3) |
S11' | 0.8163 (7) | 0.2950 (4) | 0.3095 (4) | 0.0722 (14)* | 0.215 (3) |
C13' | 0.9566 (14) | 0.1860 (9) | 0.3320 (8) | 0.0663 (19)* | 0.215 (3) |
H13' | 0.9914 | 0.1447 | 0.3495 | 0.080* | 0.215 (3) |
C14' | 1.0039 (14) | 0.2273 (9) | 0.2747 (8) | 0.0687 (19)* | 0.215 (3) |
H14' | 1.0734 | 0.2137 | 0.2522 | 0.082* | 0.215 (3) |
C15' | 0.9356 (11) | 0.2849 (8) | 0.2600 (6) | 0.068 (2)* | 0.215 (3) |
H15' | 0.9521 | 0.3157 | 0.2265 | 0.081* | 0.215 (3) |
C24 | 1.1791 (4) | −0.0510 (2) | 0.3943 (2) | 0.0761 (12) | |
H24 | 1.1499 | −0.0739 | 0.3583 | 0.091* | |
C38 | 0.7842 (4) | 0.4019 (2) | 0.72463 (19) | 0.0665 (11) | |
H38 | 0.7378 | 0.3601 | 0.7198 | 0.080* | |
C25 | 1.2842 (4) | −0.0750 (2) | 0.4228 (2) | 0.0667 (12) | |
C23 | 1.1168 (3) | 0.0070 (2) | 0.41901 (19) | 0.0625 (11) | |
H23 | 1.0460 | 0.0232 | 0.3992 | 0.075* | |
C37 | 0.7628 (5) | 0.4467 (3) | 0.7749 (2) | 0.0892 (14) | |
H37 | 0.7013 | 0.4354 | 0.8036 | 0.107* | |
C35 | 0.9191 (6) | 0.5250 (3) | 0.7406 (3) | 0.1083 (18) | |
H35 | 0.9649 | 0.5669 | 0.7460 | 0.130* | |
C34 | 0.9415 (4) | 0.4808 (3) | 0.6892 (2) | 0.0797 (13) | |
H34 | 1.0017 | 0.4932 | 0.6601 | 0.096* | |
C36 | 0.8312 (6) | 0.5078 (3) | 0.7831 (3) | 0.1050 (18) | |
H36 | 0.8175 | 0.5374 | 0.8178 | 0.126* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl21 | 0.0910 (9) | 0.1162 (10) | 0.0705 (8) | 0.0339 (7) | −0.0225 (7) | −0.0168 (7) |
Cl22 | 0.1150 (10) | 0.0628 (7) | 0.1300 (11) | 0.0048 (7) | 0.0437 (8) | −0.0204 (7) |
O21 | 0.0489 (15) | 0.0879 (19) | 0.0453 (16) | 0.0102 (14) | −0.0114 (13) | −0.0059 (14) |
N21 | 0.046 (2) | 0.061 (2) | 0.0453 (19) | −0.0011 (17) | −0.0025 (17) | −0.0016 (16) |
N2 | 0.0382 (17) | 0.065 (2) | 0.040 (2) | 0.0063 (16) | −0.0019 (16) | −0.0020 (16) |
N1 | 0.056 (2) | 0.087 (2) | 0.039 (2) | 0.0132 (18) | −0.0074 (17) | 0.0020 (17) |
N3 | 0.0498 (19) | 0.080 (2) | 0.042 (2) | 0.0140 (18) | 0.0010 (16) | −0.0066 (17) |
C21 | 0.048 (2) | 0.063 (3) | 0.047 (2) | −0.008 (2) | 0.001 (2) | −0.002 (2) |
C22 | 0.045 (2) | 0.052 (2) | 0.043 (2) | −0.008 (2) | 0.0049 (19) | 0.0014 (19) |
C2 | 0.037 (2) | 0.068 (3) | 0.044 (2) | 0.002 (2) | 0.0044 (19) | 0.002 (2) |
C26 | 0.063 (3) | 0.059 (3) | 0.076 (3) | 0.005 (2) | 0.013 (2) | 0.006 (2) |
C27 | 0.062 (3) | 0.059 (3) | 0.044 (2) | −0.001 (2) | 0.004 (2) | 0.002 (2) |
C33 | 0.048 (2) | 0.055 (3) | 0.060 (3) | 0.009 (2) | −0.003 (2) | 0.008 (2) |
C1 | 0.042 (2) | 0.073 (3) | 0.044 (2) | 0.000 (2) | 0.002 (2) | 0.004 (2) |
C31 | 0.051 (2) | 0.069 (3) | 0.044 (2) | 0.013 (2) | 0.0054 (18) | 0.003 (2) |
C32 | 0.047 (3) | 0.061 (3) | 0.052 (3) | 0.006 (2) | 0.002 (2) | 0.011 (2) |
O31 | 0.081 (2) | 0.095 (2) | 0.092 (2) | −0.0135 (17) | 0.0432 (19) | 0.0022 (17) |
C11 | 0.0467 (19) | 0.074 (2) | 0.053 (2) | −0.0016 (18) | −0.0051 (16) | 0.0004 (17) |
C12 | 0.0515 (17) | 0.0686 (19) | 0.0513 (18) | −0.0075 (16) | −0.0054 (15) | −0.0050 (16) |
S11 | 0.0475 (8) | 0.1012 (12) | 0.0653 (10) | −0.0089 (8) | 0.0079 (7) | −0.0066 (9) |
C13 | 0.064 (2) | 0.075 (2) | 0.061 (2) | −0.013 (2) | 0.000 (2) | 0.0037 (19) |
C14 | 0.077 (2) | 0.080 (2) | 0.058 (2) | −0.014 (2) | −0.001 (2) | 0.0063 (19) |
C15 | 0.069 (2) | 0.088 (2) | 0.061 (2) | −0.018 (2) | 0.0086 (19) | −0.004 (2) |
C24 | 0.083 (3) | 0.070 (3) | 0.075 (3) | −0.018 (3) | 0.010 (3) | −0.012 (3) |
C38 | 0.064 (3) | 0.073 (3) | 0.063 (3) | 0.012 (2) | 0.006 (2) | 0.001 (2) |
C25 | 0.077 (3) | 0.046 (3) | 0.077 (3) | −0.002 (2) | 0.028 (3) | −0.005 (2) |
C23 | 0.058 (3) | 0.064 (3) | 0.066 (3) | −0.006 (2) | 0.005 (2) | −0.002 (2) |
C37 | 0.105 (4) | 0.093 (4) | 0.070 (3) | 0.031 (3) | 0.016 (3) | −0.009 (3) |
C35 | 0.138 (5) | 0.075 (4) | 0.112 (5) | −0.016 (4) | −0.025 (4) | −0.022 (4) |
C34 | 0.069 (3) | 0.079 (4) | 0.091 (4) | −0.010 (3) | 0.000 (3) | 0.003 (3) |
C36 | 0.146 (5) | 0.085 (4) | 0.084 (4) | 0.032 (4) | −0.004 (4) | −0.017 (3) |
Cl21—C27 | 1.733 (4) | C12—C13 | 1.367 (8) |
Cl22—C25 | 1.733 (4) | C12—S11 | 1.692 (6) |
O21—C2 | 1.212 (4) | S11—C15 | 1.685 (5) |
N21—C21 | 1.269 (4) | C13—C14 | 1.522 (9) |
N21—N2 | 1.381 (4) | C13—H13 | 0.9300 |
N2—C1 | 1.374 (4) | C14—C15 | 1.328 (6) |
N2—C2 | 1.405 (4) | C14—H14 | 0.9300 |
N1—C1 | 1.287 (4) | C15—H15 | 0.9300 |
N1—N3 | 1.385 (4) | C12'—C13' | 1.383 (13) |
N3—C2 | 1.362 (4) | C12'—S11' | 1.698 (12) |
N3—C31 | 1.439 (4) | S11'—C15' | 1.682 (10) |
C21—C22 | 1.465 (5) | C13'—C14' | 1.526 (12) |
C21—H21 | 0.9300 | C13'—H13' | 0.9300 |
C22—C27 | 1.381 (4) | C14'—C15' | 1.337 (11) |
C22—C23 | 1.399 (5) | C14'—H14' | 0.9300 |
C26—C25 | 1.367 (5) | C15'—H15' | 0.9300 |
C26—C27 | 1.387 (5) | C24—C25 | 1.370 (5) |
C26—H26 | 0.9300 | C24—C23 | 1.374 (5) |
C33—C34 | 1.378 (5) | C24—H24 | 0.9300 |
C33—C38 | 1.383 (5) | C38—C37 | 1.372 (5) |
C33—C32 | 1.482 (5) | C38—H38 | 0.9300 |
C1—C11 | 1.489 (5) | C23—H23 | 0.9300 |
C31—C32 | 1.516 (5) | C37—C36 | 1.366 (6) |
C31—H31A | 0.9700 | C37—H37 | 0.9300 |
C31—H31B | 0.9700 | C35—C36 | 1.355 (7) |
C32—O31 | 1.204 (4) | C35—C34 | 1.386 (6) |
C11—C12 | 1.495 (5) | C35—H35 | 0.9300 |
C11—C12' | 1.522 (8) | C34—H34 | 0.9300 |
C11—H11A | 0.9700 | C36—H36 | 0.9300 |
C11—H11B | 0.9700 | ||
C21—N21—N2 | 117.5 (3) | C11—C12—S11 | 123.3 (5) |
C1—N2—N21 | 120.6 (3) | C15—S11—C12 | 92.1 (3) |
C1—N2—C2 | 108.9 (3) | C12—C13—C14 | 106.6 (5) |
N21—N2—C2 | 130.0 (3) | C12—C13—H13 | 126.7 |
C1—N1—N3 | 104.4 (3) | C14—C13—H13 | 126.7 |
C2—N3—N1 | 114.1 (3) | C15—C14—C13 | 112.9 (5) |
C2—N3—C31 | 124.5 (3) | C15—C14—H14 | 123.5 |
N1—N3—C31 | 120.8 (3) | C13—C14—H14 | 123.5 |
N21—C21—C22 | 120.2 (3) | C14—C15—S11 | 113.1 (4) |
N21—C21—H21 | 119.9 | C14—C15—H15 | 123.4 |
C22—C21—H21 | 119.9 | S11—C15—H15 | 123.4 |
C27—C22—C23 | 116.8 (3) | C13'—C12'—C11 | 119.7 (12) |
C27—C22—C21 | 121.9 (3) | C13'—C12'—S11' | 113.1 (8) |
C23—C22—C21 | 121.2 (4) | C11—C12'—S11' | 127.1 (11) |
O21—C2—N3 | 128.7 (4) | C15'—S11'—C12' | 94.1 (6) |
O21—C2—N2 | 130.3 (3) | C12'—C13'—C14' | 107.5 (10) |
N3—C2—N2 | 101.0 (3) | C12'—C13'—H13' | 126.3 |
C25—C26—C27 | 118.7 (4) | C14'—C13'—H13' | 126.3 |
C25—C26—H26 | 120.7 | C15'—C14'—C13' | 113.4 (11) |
C27—C26—H26 | 120.7 | C15'—C14'—H14' | 123.3 |
C22—C27—C26 | 122.4 (4) | C13'—C14'—H14' | 123.3 |
C22—C27—Cl21 | 120.5 (3) | C14'—C15'—S11' | 112.0 (9) |
C26—C27—Cl21 | 117.1 (3) | C14'—C15'—H15' | 124.0 |
C34—C33—C38 | 118.7 (4) | S11'—C15'—H15' | 124.0 |
C34—C33—C32 | 118.4 (4) | C25—C24—C23 | 119.9 (4) |
C38—C33—C32 | 123.0 (4) | C25—C24—H24 | 120.1 |
N1—C1—N2 | 111.5 (3) | C23—C24—H24 | 120.1 |
N1—C1—C11 | 124.2 (3) | C37—C38—C33 | 120.5 (4) |
N2—C1—C11 | 124.3 (4) | C37—C38—H38 | 119.8 |
N3—C31—C32 | 113.7 (3) | C33—C38—H38 | 119.8 |
N3—C31—H31A | 108.8 | C26—C25—C24 | 120.9 (4) |
C32—C31—H31A | 108.8 | C26—C25—Cl22 | 119.1 (4) |
N3—C31—H31B | 108.8 | C24—C25—Cl22 | 119.9 (4) |
C32—C31—H31B | 108.8 | C24—C23—C22 | 121.3 (4) |
H31A—C31—H31B | 107.7 | C24—C23—H23 | 119.3 |
O31—C32—C33 | 122.6 (4) | C22—C23—H23 | 119.3 |
O31—C32—C31 | 120.0 (3) | C36—C37—C38 | 120.5 (5) |
C33—C32—C31 | 117.4 (3) | C36—C37—H37 | 119.8 |
C1—C11—C12 | 114.9 (3) | C38—C37—H37 | 119.8 |
C1—C11—C12' | 115.8 (3) | C36—C35—C34 | 120.7 (5) |
C1—C11—H11A | 108.6 | C36—C35—H35 | 119.6 |
C12—C11—H11A | 108.6 | C34—C35—H35 | 119.6 |
C12'—C11—H11A | 112.3 | C33—C34—C35 | 119.9 (5) |
C1—C11—H11B | 108.6 | C33—C34—H34 | 120.0 |
C12—C11—H11B | 108.6 | C35—C34—H34 | 120.0 |
C12'—C11—H11B | 103.7 | C35—C36—C37 | 119.7 (5) |
H11A—C11—H11B | 107.5 | C35—C36—H36 | 120.2 |
C13—C12—C11 | 121.4 (5) | C37—C36—H36 | 120.2 |
C13—C12—S11 | 115.1 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C21—H21···O21 | 0.93 | 2.23 | 2.916 (4) | 130 |
C13—H13···O21i | 0.93 | 2.53 | 3.355 (7) | 148 |
Symmetry code: (i) x−1/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C22H16Cl2N4O2S |
Mr | 471.35 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 10.9045 (13), 18.509 (2), 21.228 (3) |
V (Å3) | 4284.4 (9) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.43 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20905, 5052, 1671 |
Rint | 0.103 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.131, 0.84 |
No. of reflections | 5052 |
No. of parameters | 301 |
No. of restraints | 148 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.25 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
C21—H21···O21 | 0.93 | 2.231 | 2.916 (4) | 130 |
C13—H13···O21i | 0.93 | 2.532 | 3.355 (7) | 148 |
Symmetry code: (i) x−1/2, −y+1/2, −z+1. |
1,2,4 triazole and 1,2,4 triazole-5-one derivatives have pharmacological properties as antimicrobial (Holla et al., 1998; Ersan et al., 1998; İkizler et al., 1999), anti imflammatory, analgesic, antitumorial, antihypertensive, antiviral activities, coccidiostatic (Tozkoparan et al., 2000; Turan-Zitouni et al.; 1999, Holla et al., 2002). It was reported that compounds having triazole moieties such as Vorozole, Anastrozole and Letrozole appear to be very effective aromatase inhibitors very useful for preventing breast cancer (Goss et al., 2004, Santen 2003, Clemons et al., 2004). Spectroscopic and crystal structure data of some di-1,2,4-triazole-5-ones have been reported previously (Sancak et al., 2005).
The compound was prepared and first identifed by NMR spectroscopy. In order to confirm the geometry, its X-ray structure determination was carried out. Compound (I) contains four planar rings (Fig. 1), namely two benzene rings [C22—C27 (A) and C33—C38 (B)], a triazole ring (C) and a thiophene ring (D). Deviations from the ideal bond-angle geometry around the Nsp2 atoms of the single bond are observed. The N21—N2—C1 and N1—N3—C31 bond angles are 120.6 (3)° and 120.8 (3)°, respectively, too close to the ideal geometry (120°); however, the N21—N2—C2, C2—N3—C31 and N1—N3—C2 angles [130 (3)°, 124.5 (3)° and 114.1 (3)°, respectively] are distorted. In the triazole ring atom C2 deviate significantly from planarity. We can conclude, that the reason for these two deviation is intramolecular and intermolecular hydrogen bonds with the O21 atom.
The N21═C21 bond length [1.269 (4) Å] agree with values reported in the literature [1.261 (4) Å in the 4-amino-3-methtl-1,2,4-triazole- 5-thione derivative of p-nitrobenzaldehyde (Liu et al., 1999), 1.267 (2) Å in 4-(4-hydroxybenzylidenamino)-4H-1,2,4-triazole hemihydrate (Zhu et al., 2000) and 1.271 (3) Å in the 1-acetyl-4- (p-chlorobenzylideneamino)-3-methyl-4,5-dihydro-1H-1,2,4-triazol-5-one (Çoruh et al., 2003)]. The presence of a substituent on N3 causes a lengthening of the N—N bond length [N1—N3= 1.385 (4) Å] with respect to the corresponding bonds in 5-(2-chlorophenyl)-4-phenyl-3,4-dihydro-2H-1,2,4-triazole-3-thione [N—N= 1.374 (2) Å; Puviarasan et al., 1999] and in 4-methyl-1,2,4- triazole and 1-methyltetrazole [N—N= 1.344 (2) Å; Palmer & Parsons, 1996]. The S—C bond lengths [S11—C12= 1.692 (6) Å and S11—C15= 1.685 (5) Å] agree with value reported in the literature (Vrábel et al., 2005; Yılmaz et al., 2006)].
The thiophene ring is disordered over two positions, corresponding to rotation of approximately 180° about the single C11—C12 bond, with a major-minor ratio of about 78.5:21.5. Such flip-type disorder is rather common in thiophene rings. Weak C—H···O hydrogen bonds may help in stabilizing the crystal structure.