Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053329/hk2353sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053329/hk2353Isup2.hkl |
CCDC reference: 672788
The synthesis of the title compound was carried out by refluxing a solution of 1-(3-(3-methoxyphenyl)propanoyl)-4-(4-chlorophenyl)thiosemicarbazide (3.63 g, 10 mmol) in NaOH (2 M) for 5 h. Single crystals suitable for X-ray analysis were obtained by recrystallization from an aqeous ethanol solution at room temperature (yield; 72%, m.p. 461–462 K).
The H atom (for SH) was located in difference syntheses, and constrained to ride on its parent atom, with S—H = 0.9972 Å and Uiso = 1.5Ueq(S). The remaining H atoms were positioned geometrically, with C—H = 0.95, 0.99 and 0.98 Å for aromatic, methylene and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.
Data collection: COLLECT (Bruker, 2000); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2007); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C17H16ClN3OS | Z = 2 |
Mr = 345.84 | F(000) = 360 |
Triclinic, P1 | Dx = 1.399 Mg m−3 |
Hall symbol: -P 1 | Melting point: 461(1) K |
a = 7.1697 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.1376 (4) Å | Cell parameters from 9213 reflections |
c = 11.7574 (5) Å | θ = 1.0–27.5° |
α = 67.070 (2)° | µ = 0.37 mm−1 |
β = 77.421 (2)° | T = 120 K |
γ = 72.948 (3)° | Block, colorless |
V = 820.93 (6) Å3 | 0.26 × 0.18 × 0.13 mm |
Nonius KappaCCD diffractometer | 3752 independent reflections |
Radiation source: fine-focus sealed tube | 2725 reflections with I > 2σ(I) |
Horizontally mounted graphite crystal monochromator | Rint = 0.048 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 1.9° |
ϕ scans and ω scans with κ offset | h = −9→9 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −14→14 |
Tmin = 0.912, Tmax = 0.953 | l = −15→15 |
15238 measured reflections |
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)] = 0.043 | Hydrogen site location: mixed |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0467P)2 + 0.5947P] where P = (Fo2 + 2Fc2)/3 |
3752 reflections | (Δ/σ)max < 0.001 |
209 parameters | Δρmax = 0.74 e Å−3 |
0 restraints | Δρmin = −0.77 e Å−3 |
C17H16ClN3OS | γ = 72.948 (3)° |
Mr = 345.84 | V = 820.93 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.1697 (3) Å | Mo Kα radiation |
b = 11.1376 (4) Å | µ = 0.37 mm−1 |
c = 11.7574 (5) Å | T = 120 K |
α = 67.070 (2)° | 0.26 × 0.18 × 0.13 mm |
β = 77.421 (2)° |
Nonius KappaCCD diffractometer | 3752 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2725 reflections with I > 2σ(I) |
Tmin = 0.912, Tmax = 0.953 | Rint = 0.048 |
15238 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.74 e Å−3 |
3752 reflections | Δρmin = −0.77 e Å−3 |
209 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 | ||
Cl1 | 0.76936 (8) | 0.01723 (5) | 0.38434 (5) | 0.02439 (16) | |
S1 | 1.42541 (8) | −0.32374 (5) | 0.81974 (5) | 0.02415 (16) | |
H1S | 1.4839 | −0.3213 | 0.8882 | 0.036* | |
O1 | 0.3991 (2) | −0.62525 (16) | 0.62402 (16) | 0.0305 (4) | |
N1 | 1.1468 (2) | −0.43495 (17) | 0.79786 (15) | 0.0162 (4) | |
N2 | 1.3112 (3) | −0.55857 (17) | 0.95049 (16) | 0.0186 (4) | |
N3 | 1.1823 (3) | −0.63067 (17) | 0.95225 (16) | 0.0192 (4) | |
C1 | 0.8828 (3) | −0.1146 (2) | 0.5053 (2) | 0.0182 (5) | |
C2 | 1.0559 (3) | −0.1999 (2) | 0.4786 (2) | 0.0201 (5) | |
H2 | 1.1130 | −0.1859 | 0.3949 | 0.024* | |
C3 | 1.1453 (3) | −0.3063 (2) | 0.5751 (2) | 0.0193 (5) | |
H3 | 1.2630 | −0.3667 | 0.5583 | 0.023* | |
C4 | 1.0604 (3) | −0.3228 (2) | 0.69584 (19) | 0.0162 (4) | |
C5 | 0.8906 (3) | −0.2357 (2) | 0.7231 (2) | 0.0203 (5) | |
H5 | 0.8371 | −0.2475 | 0.8071 | 0.024* | |
C6 | 0.7986 (3) | −0.1308 (2) | 0.6265 (2) | 0.0211 (5) | |
H6 | 0.6800 | −0.0710 | 0.6434 | 0.025* | |
C7 | 1.2942 (3) | −0.4394 (2) | 0.85785 (19) | 0.0180 (5) | |
C8 | 1.0843 (3) | −0.5532 (2) | 0.85786 (19) | 0.0175 (4) | |
C9 | 0.9291 (3) | −0.5843 (2) | 0.8159 (2) | 0.0203 (5) | |
H9A | 0.9608 | −0.5699 | 0.7260 | 0.024* | |
H9B | 0.8021 | −0.5219 | 0.8278 | 0.024* | |
C10 | 0.9083 (3) | −0.7281 (2) | 0.8865 (2) | 0.0226 (5) | |
H10A | 1.0385 | −0.7895 | 0.8802 | 0.027* | |
H10B | 0.8676 | −0.7398 | 0.9755 | 0.027* | |
C11 | 0.7628 (3) | −0.7685 (2) | 0.8412 (2) | 0.0209 (5) | |
C12 | 0.6384 (3) | −0.6796 (2) | 0.7539 (2) | 0.0211 (5) | |
H12 | 0.6405 | −0.5874 | 0.7214 | 0.025* | |
C13 | 0.5102 (3) | −0.7227 (2) | 0.7129 (2) | 0.0224 (5) | |
C14 | 0.5016 (3) | −0.8572 (2) | 0.7609 (2) | 0.0258 (5) | |
H14 | 0.4141 | −0.8872 | 0.7336 | 0.031* | |
C15 | 0.6245 (4) | −0.9462 (2) | 0.8498 (2) | 0.0301 (6) | |
H15 | 0.6197 | −1.0380 | 0.8840 | 0.036* | |
C16 | 0.7531 (4) | −0.9040 (2) | 0.8892 (2) | 0.0283 (5) | |
H16 | 0.8363 | −0.9671 | 0.9495 | 0.034* | |
C17 | 0.2965 (4) | −0.6684 (3) | 0.5611 (3) | 0.0376 (6) | |
H17A | 0.3901 | −0.7301 | 0.5230 | 0.056* | |
H17B | 0.2303 | −0.5905 | 0.4963 | 0.056* | |
H17C | 0.1988 | −0.7143 | 0.6208 | 0.056* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0265 (3) | 0.0187 (3) | 0.0252 (3) | −0.0051 (2) | −0.0144 (2) | 0.0011 (2) |
S1 | 0.0245 (3) | 0.0206 (3) | 0.0261 (3) | −0.0096 (2) | −0.0142 (2) | 0.0023 (2) |
O1 | 0.0293 (9) | 0.0269 (9) | 0.0428 (10) | −0.0037 (7) | −0.0177 (8) | −0.0150 (8) |
N1 | 0.0168 (9) | 0.0155 (9) | 0.0157 (9) | −0.0046 (7) | −0.0057 (7) | −0.0021 (7) |
N2 | 0.0191 (9) | 0.0168 (9) | 0.0203 (9) | −0.0069 (7) | −0.0059 (7) | −0.0029 (7) |
N3 | 0.0207 (9) | 0.0184 (9) | 0.0190 (9) | −0.0060 (7) | −0.0052 (7) | −0.0045 (7) |
C1 | 0.0217 (11) | 0.0132 (10) | 0.0212 (11) | −0.0070 (8) | −0.0105 (9) | −0.0011 (8) |
C2 | 0.0223 (11) | 0.0201 (11) | 0.0182 (11) | −0.0045 (9) | −0.0053 (9) | −0.0059 (9) |
C3 | 0.0181 (11) | 0.0185 (11) | 0.0210 (11) | −0.0029 (8) | −0.0049 (9) | −0.0062 (9) |
C4 | 0.0162 (10) | 0.0143 (10) | 0.0187 (10) | −0.0057 (8) | −0.0076 (8) | −0.0019 (8) |
C5 | 0.0198 (11) | 0.0204 (11) | 0.0186 (11) | −0.0054 (9) | −0.0019 (9) | −0.0043 (9) |
C6 | 0.0165 (11) | 0.0199 (11) | 0.0255 (12) | −0.0035 (8) | −0.0036 (9) | −0.0062 (9) |
C7 | 0.0157 (10) | 0.0190 (11) | 0.0175 (10) | −0.0021 (8) | −0.0041 (8) | −0.0046 (9) |
C8 | 0.0186 (11) | 0.0162 (10) | 0.0164 (10) | −0.0054 (8) | −0.0025 (8) | −0.0032 (8) |
C9 | 0.0214 (11) | 0.0198 (11) | 0.0211 (11) | −0.0071 (9) | −0.0074 (9) | −0.0044 (9) |
C10 | 0.0265 (12) | 0.0213 (11) | 0.0211 (11) | −0.0086 (9) | −0.0065 (9) | −0.0045 (9) |
C11 | 0.0219 (11) | 0.0212 (11) | 0.0212 (11) | −0.0087 (9) | 0.0012 (9) | −0.0084 (9) |
C12 | 0.0226 (11) | 0.0198 (11) | 0.0237 (11) | −0.0073 (9) | −0.0023 (9) | −0.0091 (9) |
C13 | 0.0189 (11) | 0.0255 (12) | 0.0250 (12) | −0.0040 (9) | −0.0010 (9) | −0.0128 (10) |
C14 | 0.0257 (12) | 0.0286 (13) | 0.0310 (13) | −0.0120 (10) | −0.0002 (10) | −0.0162 (10) |
C15 | 0.0362 (14) | 0.0234 (12) | 0.0333 (14) | −0.0146 (11) | −0.0014 (11) | −0.0084 (11) |
C16 | 0.0331 (13) | 0.0231 (12) | 0.0281 (13) | −0.0109 (10) | −0.0077 (11) | −0.0030 (10) |
C17 | 0.0365 (15) | 0.0410 (15) | 0.0469 (16) | −0.0090 (12) | −0.0200 (13) | −0.0197 (13) |
Cl1—C1 | 1.737 (2) | C8—C9 | 1.483 (3) |
S1—C7 | 1.680 (2) | C9—C10 | 1.525 (3) |
S1—H1S | 0.9972 | C9—H9A | 0.9900 |
O1—C13 | 1.370 (3) | C9—H9B | 0.9900 |
O1—C17 | 1.429 (3) | C10—C11 | 1.509 (3) |
N1—C7 | 1.372 (3) | C10—H10A | 0.9900 |
N1—C8 | 1.385 (3) | C10—H10B | 0.9900 |
N1—C4 | 1.444 (2) | C11—C12 | 1.384 (3) |
N2—C7 | 1.341 (3) | C11—C16 | 1.408 (3) |
N2—N3 | 1.384 (2) | C12—C13 | 1.393 (3) |
N3—C8 | 1.307 (3) | C12—H12 | 0.9500 |
C1—C2 | 1.383 (3) | C13—C14 | 1.396 (3) |
C1—C6 | 1.384 (3) | C14—C15 | 1.390 (3) |
C2—C3 | 1.387 (3) | C14—H14 | 0.9500 |
C2—H2 | 0.9500 | C15—C16 | 1.377 (3) |
C3—C4 | 1.380 (3) | C15—H15 | 0.9500 |
C3—H3 | 0.9500 | C16—H16 | 0.9500 |
C4—C5 | 1.381 (3) | C17—H17A | 0.9800 |
C5—C6 | 1.390 (3) | C17—H17B | 0.9800 |
C5—H5 | 0.9500 | C17—H17C | 0.9800 |
C6—H6 | 0.9500 | ||
C7—S1—H1S | 116.9 | C8—C9—H9B | 109.1 |
C13—O1—C17 | 117.19 (18) | C10—C9—H9B | 109.1 |
C7—N1—C8 | 108.24 (16) | H9A—C9—H9B | 107.9 |
C7—N1—C4 | 126.25 (17) | C11—C10—C9 | 114.60 (18) |
C8—N1—C4 | 125.36 (17) | C11—C10—H10A | 108.6 |
C7—N2—N3 | 113.38 (17) | C9—C10—H10A | 108.6 |
C8—N3—N2 | 104.10 (16) | C11—C10—H10B | 108.6 |
C2—C1—C6 | 121.58 (19) | C9—C10—H10B | 108.6 |
C2—C1—Cl1 | 119.36 (17) | H10A—C10—H10B | 107.6 |
C6—C1—Cl1 | 119.05 (17) | C12—C11—C16 | 117.8 (2) |
C1—C2—C3 | 119.4 (2) | C12—C11—C10 | 123.64 (19) |
C1—C2—H2 | 120.3 | C16—C11—C10 | 118.5 (2) |
C3—C2—H2 | 120.3 | C11—C12—C13 | 121.4 (2) |
C4—C3—C2 | 119.0 (2) | C11—C12—H12 | 119.3 |
C4—C3—H3 | 120.5 | C13—C12—H12 | 119.3 |
C2—C3—H3 | 120.5 | O1—C13—C12 | 115.4 (2) |
C3—C4—C5 | 121.81 (19) | O1—C13—C14 | 124.1 (2) |
C3—C4—N1 | 120.17 (18) | C12—C13—C14 | 120.5 (2) |
C5—C4—N1 | 118.01 (19) | C15—C14—C13 | 118.2 (2) |
C4—C5—C6 | 119.3 (2) | C15—C14—H14 | 120.9 |
C4—C5—H5 | 120.3 | C13—C14—H14 | 120.9 |
C6—C5—H5 | 120.3 | C16—C15—C14 | 121.3 (2) |
C1—C6—C5 | 118.9 (2) | C16—C15—H15 | 119.3 |
C1—C6—H6 | 120.6 | C14—C15—H15 | 119.3 |
C5—C6—H6 | 120.6 | C15—C16—C11 | 120.8 (2) |
N2—C7—N1 | 103.63 (18) | C15—C16—H16 | 119.6 |
N2—C7—S1 | 128.85 (16) | C11—C16—H16 | 119.6 |
N1—C7—S1 | 127.50 (15) | O1—C17—H17A | 109.5 |
N3—C8—N1 | 110.66 (18) | O1—C17—H17B | 109.5 |
N3—C8—C9 | 126.37 (18) | H17A—C17—H17B | 109.5 |
N1—C8—C9 | 122.96 (18) | O1—C17—H17C | 109.5 |
C8—C9—C10 | 112.31 (17) | H17A—C17—H17C | 109.5 |
C8—C9—H9A | 109.1 | H17B—C17—H17C | 109.5 |
C10—C9—H9A | 109.1 |
D—H···A | D—H | H···A | D···A | D—H···A |
S1—H1S···N2i | 1.00 | 2.37 | 3.2546 (18) | 147 |
Symmetry code: (i) −x+3, −y−1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C17H16ClN3OS |
Mr | 345.84 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 120 |
a, b, c (Å) | 7.1697 (3), 11.1376 (4), 11.7574 (5) |
α, β, γ (°) | 67.070 (2), 77.421 (2), 72.948 (3) |
V (Å3) | 820.93 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.37 |
Crystal size (mm) | 0.26 × 0.18 × 0.13 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.912, 0.953 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15238, 3752, 2725 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.111, 1.04 |
No. of reflections | 3752 |
No. of parameters | 209 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.74, −0.77 |
Computer programs: COLLECT (Bruker, 2000), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2007).
D—H···A | D—H | H···A | D···A | D—H···A |
S1—H1S···N2i | 1.00 | 2.37 | 3.2546 (18) | 147.0 |
Symmetry code: (i) −x+3, −y−1, −z+2. |
Substituted triazole derivatives display significant biological activities including antimicrobial (Holla et al., 1998), analgesic (Turan-Zitouni et al., 1999), antitumor (Demirbas et al., 2002), antihypertensive (Paulvannan et al., 2000) and antiviral activities (Kritsanida et al., 2002). The biological activity is closely related to the structure, possibly being due to the presence of the —N—C ═S unit (Omar et al., 1986). We are interested in the synthesis and biological activities of aryloxyacetyl hydrazide derivatives and report herein the synthesis and crystal structure of the title compound, (I).
In the molecule of the title compound, (I), (Fig. 1) the bond lengths and angles are comparable with those observed in related structures (Öztürk et al., 2004a,b). The C1═S1 [1.680 (2) Å] bond agrees with the corresponding values [1.6773 (19) Å] in 4-(4-chlorophenyl)-3-(furan-2-yl)-1H-1,2,4-triazole-5(4H)-thione (Öztürk et al., 2004a) and [1.668 (5) Å] in 4-amino-3-(1,2,3,4,5-pentahydroxypentyl)-1H-1,2,4-triazole-5(4H)-thione (Zhang et al., 2004). In the triazole ring, the N2 ═C2 [1.347 (3) Å] bond has double-bond character. The planar triazole ring A (N1–N3/C7/C8) is oriented with respect to planar 4-chlorophenyl and 2-(3-methoxyphenyl)ethyl rings; B (C1–C6) and C (C11–C16), at dihedral angles of 89.5 (1) and 56.9 (1)°, respectively. The dihedral angle between rings B and C is B/C = 78.5 (1)°.
In the crystal structure, intermolecular N—H···S hydrogen bonds (Table 1, Fig. 2) link the molecules, in which they seem to be effective in the stabilization of the structure.