organic compounds
4-Ethyl-3-(3-pyridyl)-1H-1,2,4-triazole-5(4H)-thione 0.095-hydrate
aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, and bDepartment of Chemistry, The University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4
*Correspondence e-mail: mzareef71@yahoo.com
The title compound, C9H10N4S·0.095H2O, consists of discrete 4-ethyl-3-(3-pyridyl)-1H-1,2,4-triazole-5(4H)-thione molecules and a disordered molecule of water of hydration with partial occupancy, lying on a twofold rotation axis. The dihedral angle between the pyridine and triazole rings is 41.73 (8)°. In the molecules are hydrogen bonded via triazole NH groups and pyridyl N atoms, forming chains parallel to the a axis.
Related literature
For related literature, see: Ahmad et al. (2001); Chai et al. (2003); Dege et al. (2004, 2005)); Demir et al. (2006); Dobosz et al. (2003); Hashimoto et al. (1990); Kanazawa et al. (1988); Mazur et al. (2006).
Experimental
Crystal data
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Refinement
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Data collection: COLLECT (Hooft, 1998); cell DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536808011744/lh2615sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808011744/lh2615Isup2.hkl
The title compound was prepared from the corresponding thiosemicarbazide by following the reported procedure (Ahmad et al., 2001). 4-Ethyl-1-(2-pyridoyl)thiosemicarbazide (12 mmol) was dissolved in an aqueous 4 N sodium hydroxide solution (65 ml). The solution was heated to reflux for 11.5 h, cooled and filtered. The filtrate was acidified to pH of 4–5, with 4 N hydrochloric acid. The solid product was filtered off, washed with water and recrystallized from aqueous ethanol (60%). Crystals of (I) were grown by slow evaporation of the ethanol over 15 days at room temperature (yield 72%).
Though all the H atoms could be distinguished in the difference Fourier map the H-atoms bonded to C-atoms were included at geometrically idealized positions and refined in riding-model approximation with the following constraints: pyridyl, methyl and methylene C—H distances were set to 0.95, 0.98 and 0.99 Å, respectively; in all these instances Uiso(H) = 1.2 Ueq(C). H-atom bonded to N2 was taken from the difference map and was allowed to refine with Uiso = 1.2 times Ueq of N2. Towards the end of the
a difference Fourier map revealed a peak that was included in the as an O-atom the site occupancy factor of which refined to 0.095; its s.o.f. was fixed at that value during the final rounds of calculations. The H-atoms bonded to the O atom of the water molecule could not be located and were not included in the but are included in the The atmospheric moisture was assumed to be the source of this partially occupied water of hydration. The final difference map was free of any chemically significant features.Data collection: COLLECT (Hooft, 1998); cell
DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C9H10N4S·0.095H2O | F(000) = 872 |
Mr = 207.96 | Dx = 1.366 Mg m−3 |
Monoclinic, C2/c | Melting point = 440–441 K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 14.076 (5) Å | Cell parameters from 3392 reflections |
b = 8.877 (5) Å | θ = 3.6–27.4° |
c = 16.216 (8) Å | µ = 0.29 mm−1 |
β = 93.25 (3)° | T = 173 K |
V = 2023.0 (17) Å3 | Block, colorless |
Z = 8 | 0.18 × 0.16 × 0.10 mm |
Nonius KappaCCD diffractometer | 2297 independent reflections |
Radiation source: fine-focus sealed tube | 1616 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω and ϕ scans | θmax = 27.4°, θmin = 3.6° |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | h = −17→18 |
Tmin = 0.950, Tmax = 0.972 | k = −11→9 |
3392 measured reflections | l = −20→20 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.107 | w = 1/[σ2(Fo2) + (0.0405P)2 + 1.636P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2297 reflections | Δρmax = 0.24 e Å−3 |
137 parameters | Δρmin = −0.25 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0038 (9) |
C9H10N4S·0.095H2O | V = 2023.0 (17) Å3 |
Mr = 207.96 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 14.076 (5) Å | µ = 0.29 mm−1 |
b = 8.877 (5) Å | T = 173 K |
c = 16.216 (8) Å | 0.18 × 0.16 × 0.10 mm |
β = 93.25 (3)° |
Nonius KappaCCD diffractometer | 2297 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | 1616 reflections with I > 2σ(I) |
Tmin = 0.950, Tmax = 0.972 | Rint = 0.030 |
3392 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.24 e Å−3 |
2297 reflections | Δρmin = −0.25 e Å−3 |
137 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) | |
S1 | −0.12974 (4) | 0.05644 (7) | −0.11164 (3) | 0.0415 (2) | |
O1 | 0.0000 | −0.0319 (16) | −0.2500 | 0.070 (4) | 0.19 |
N1 | −0.07296 (10) | 0.26787 (18) | 0.09536 (9) | 0.0256 (4) | |
N2 | −0.13013 (11) | 0.19176 (19) | 0.03795 (10) | 0.0276 (4) | |
H2 | −0.1854 (16) | 0.158 (3) | 0.0530 (12) | 0.033* | |
N3 | 0.00251 (10) | 0.22103 (18) | −0.01818 (9) | 0.0228 (4) | |
N4 | 0.21945 (11) | 0.53359 (19) | 0.10227 (10) | 0.0290 (4) | |
C1 | 0.00713 (12) | 0.2838 (2) | 0.05951 (10) | 0.0217 (4) | |
C2 | −0.08639 (13) | 0.1576 (2) | −0.03071 (12) | 0.0267 (4) | |
C3 | 0.14695 (12) | 0.4604 (2) | 0.06268 (11) | 0.0246 (4) | |
H3 | 0.1343 | 0.4794 | 0.0055 | 0.029* | |
C4 | 0.08963 (12) | 0.3582 (2) | 0.10142 (11) | 0.0220 (4) | |
C5 | 0.10899 (13) | 0.3310 (2) | 0.18541 (11) | 0.0263 (4) | |
H5 | 0.0714 | 0.2616 | 0.2140 | 0.032* | |
C6 | 0.18343 (14) | 0.4061 (2) | 0.22654 (12) | 0.0313 (5) | |
H6 | 0.1977 | 0.3897 | 0.2838 | 0.038* | |
C7 | 0.23642 (13) | 0.5050 (2) | 0.18282 (12) | 0.0313 (5) | |
H7 | 0.2878 | 0.5559 | 0.2113 | 0.038* | |
C8 | 0.07912 (14) | 0.1998 (2) | −0.07478 (12) | 0.0300 (5) | |
H8A | 0.0756 | 0.0962 | −0.0973 | 0.036* | |
H8B | 0.1412 | 0.2110 | −0.0436 | 0.036* | |
C9 | 0.07367 (17) | 0.3113 (3) | −0.14570 (13) | 0.0406 (6) | |
H9A | 0.1216 | 0.2857 | −0.1849 | 0.049* | |
H9B | 0.0856 | 0.4132 | −0.1243 | 0.049* | |
H9C | 0.0102 | 0.3072 | −0.1738 | 0.049* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0476 (4) | 0.0346 (4) | 0.0398 (3) | −0.0034 (3) | −0.0202 (3) | −0.0060 (2) |
O1 | 0.107 (12) | 0.043 (9) | 0.063 (9) | 0.000 | 0.034 (9) | 0.000 |
N1 | 0.0194 (8) | 0.0271 (10) | 0.0300 (8) | −0.0060 (7) | −0.0022 (6) | 0.0005 (7) |
N2 | 0.0201 (8) | 0.0283 (10) | 0.0339 (9) | −0.0080 (7) | −0.0032 (7) | 0.0017 (7) |
N3 | 0.0228 (8) | 0.0221 (9) | 0.0232 (8) | −0.0008 (7) | −0.0026 (6) | 0.0016 (6) |
N4 | 0.0220 (8) | 0.0282 (10) | 0.0367 (9) | −0.0042 (7) | 0.0002 (7) | 0.0000 (7) |
C1 | 0.0209 (9) | 0.0215 (10) | 0.0225 (9) | −0.0007 (8) | −0.0008 (7) | 0.0031 (7) |
C2 | 0.0256 (10) | 0.0221 (11) | 0.0315 (10) | −0.0015 (8) | −0.0076 (8) | 0.0044 (8) |
C3 | 0.0199 (9) | 0.0269 (11) | 0.0267 (9) | −0.0012 (8) | −0.0001 (7) | 0.0024 (8) |
C4 | 0.0180 (9) | 0.0212 (10) | 0.0267 (9) | −0.0001 (7) | 0.0005 (7) | −0.0007 (8) |
C5 | 0.0234 (10) | 0.0288 (11) | 0.0268 (9) | −0.0024 (8) | 0.0027 (7) | −0.0005 (8) |
C6 | 0.0298 (10) | 0.0399 (13) | 0.0237 (9) | −0.0020 (9) | −0.0034 (8) | −0.0027 (9) |
C7 | 0.0226 (10) | 0.0333 (12) | 0.0373 (11) | −0.0047 (9) | −0.0052 (8) | −0.0081 (9) |
C8 | 0.0316 (10) | 0.0289 (12) | 0.0299 (10) | 0.0029 (9) | 0.0044 (8) | −0.0006 (9) |
C9 | 0.0540 (14) | 0.0397 (14) | 0.0289 (11) | 0.0010 (11) | 0.0096 (10) | 0.0024 (10) |
S1—C2 | 1.676 (2) | C3—C4 | 1.388 (3) |
S1—O1 | 3.074 (4) | C3—H3 | 0.9500 |
O1—S1i | 3.074 (4) | C4—C5 | 1.395 (3) |
O1—N1ii | 3.382 (9) | C5—C6 | 1.381 (3) |
N1—C1 | 1.305 (2) | C5—H5 | 0.9500 |
N1—N2 | 1.373 (2) | C6—C7 | 1.375 (3) |
N2—C2 | 1.337 (3) | C6—H6 | 0.9500 |
N2—H2 | 0.88 (2) | C7—H7 | 0.9500 |
N3—C1 | 1.376 (2) | C8—C9 | 1.516 (3) |
N3—C2 | 1.377 (2) | C8—H8A | 0.9900 |
N3—C8 | 1.467 (2) | C8—H8B | 0.9900 |
N4—C7 | 1.339 (3) | C9—H9A | 0.9800 |
N4—C3 | 1.342 (2) | C9—H9B | 0.9800 |
C1—C4 | 1.469 (2) | C9—H9C | 0.9800 |
C2—S1—O1 | 120.21 (15) | C5—C4—C1 | 118.66 (16) |
S1—O1—S1i | 150.4 (5) | C6—C5—C4 | 119.26 (18) |
S1—O1—N1ii | 77.57 (10) | C6—C5—H5 | 120.4 |
S1i—O1—N1ii | 122.08 (18) | C4—C5—H5 | 120.4 |
C1—N1—N2 | 103.82 (16) | C7—C6—C5 | 118.57 (18) |
C2—N2—N1 | 113.35 (16) | C7—C6—H6 | 120.7 |
C2—N2—H2 | 127.4 (14) | C5—C6—H6 | 120.7 |
N1—N2—H2 | 118.2 (14) | N4—C7—C6 | 123.51 (17) |
C1—N3—C2 | 107.22 (15) | N4—C7—H7 | 118.2 |
C1—N3—C8 | 128.79 (15) | C6—C7—H7 | 118.2 |
C2—N3—C8 | 123.33 (16) | N3—C8—C9 | 112.54 (17) |
C7—N4—C3 | 117.62 (17) | N3—C8—H8A | 109.1 |
N1—C1—N3 | 111.53 (16) | C9—C8—H8A | 109.1 |
N1—C1—C4 | 121.52 (16) | N3—C8—H8B | 109.1 |
N3—C1—C4 | 126.94 (16) | C9—C8—H8B | 109.1 |
N2—C2—N3 | 104.00 (16) | H8A—C8—H8B | 107.8 |
N2—C2—S1 | 127.52 (15) | C8—C9—H9A | 109.5 |
N3—C2—S1 | 128.46 (16) | C8—C9—H9B | 109.5 |
N4—C3—C4 | 123.08 (17) | H9A—C9—H9B | 109.5 |
N4—C3—H3 | 118.5 | C8—C9—H9C | 109.5 |
C4—C3—H3 | 118.5 | H9A—C9—H9C | 109.5 |
C3—C4—C5 | 117.95 (16) | H9B—C9—H9C | 109.5 |
C3—C4—C1 | 123.31 (16) | ||
C2—S1—O1—S1i | −60.83 (15) | O1—S1—C2—N3 | 5.5 (3) |
C2—S1—O1—N1ii | 74.7 (3) | C7—N4—C3—C4 | 0.2 (3) |
C1—N1—N2—C2 | 1.6 (2) | N4—C3—C4—C5 | −0.1 (3) |
N2—N1—C1—N3 | 0.1 (2) | N4—C3—C4—C1 | 176.65 (18) |
N2—N1—C1—C4 | −178.76 (16) | N1—C1—C4—C3 | −137.4 (2) |
C2—N3—C1—N1 | −1.8 (2) | N3—C1—C4—C3 | 43.9 (3) |
C8—N3—C1—N1 | −172.57 (17) | N1—C1—C4—C5 | 39.3 (3) |
C2—N3—C1—C4 | 177.06 (18) | N3—C1—C4—C5 | −139.4 (2) |
C8—N3—C1—C4 | 6.3 (3) | C3—C4—C5—C6 | 0.2 (3) |
N1—N2—C2—N3 | −2.7 (2) | C1—C4—C5—C6 | −176.73 (18) |
N1—N2—C2—S1 | 175.75 (14) | C4—C5—C6—C7 | −0.3 (3) |
C1—N3—C2—N2 | 2.6 (2) | C3—N4—C7—C6 | −0.4 (3) |
C8—N3—C2—N2 | 174.01 (16) | C5—C6—C7—N4 | 0.4 (3) |
C1—N3—C2—S1 | −175.82 (15) | C1—N3—C8—C9 | −105.1 (2) |
C8—N3—C2—S1 | −4.4 (3) | C2—N3—C8—C9 | 85.4 (2) |
O1—S1—C2—N2 | −172.6 (3) |
Symmetry codes: (i) −x, y, −z−1/2; (ii) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···N4iii | 0.88 (2) | 1.94 (2) | 2.792 (3) | 162 (2) |
Symmetry code: (iii) x−1/2, y−1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C9H10N4S·0.095H2O |
Mr | 207.96 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 173 |
a, b, c (Å) | 14.076 (5), 8.877 (5), 16.216 (8) |
β (°) | 93.25 (3) |
V (Å3) | 2023.0 (17) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.29 |
Crystal size (mm) | 0.18 × 0.16 × 0.10 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1997) |
Tmin, Tmax | 0.950, 0.972 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3392, 2297, 1616 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.647 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.107, 1.05 |
No. of reflections | 2297 |
No. of parameters | 137 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.25 |
Computer programs: COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997), SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···N4i | 0.88 (2) | 1.94 (2) | 2.792 (3) | 162 (2) |
Symmetry code: (i) x−1/2, y−1/2, z. |
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Disubstituted 1,2,4-triazoles and their derivatives are very important five membered heterocyclic compounds for their biological and pharmacological activities, such as antitumoral, inhibition of cholesterol, fungicidal, herbicidal, anticonvulsant (Kanazawa et al., 1988; Chai et al., 2003; Hashimoto et al., 1990). Herein, we report the synthesis and crystal structure of the title compound, (I).
The structure of (I) is composed of independent molecules of 4-ethyl-2,4-dihydro-5-(3-pyridyl)-3H-1,2,4-triazole-3-thione (Fig. 1) and a disordered water of hydration with partial occupancy lying on a two-fold rotation axis. The bond distances and bond angles in (I) agree well with the corresponding bond distances and angles reported in some compounds closely related to (I) (e.g., Dege et al., 2004, 2005; Mazur et al., 2006; Dobosz et al., 2003; Demir, et al., 2006). The mean-planes formed by the pyridyl and triazole rings in (I) lie at 41.73 (8)° with respect to each other while the mean-plane of the ethyl group is inclined with the triazole ring at 80.39 (13)°.
The water of hydration is surrounded by four molecules of (I) with S1···O1 and N1···O1 separation of 3.074 (4) and 3.382 (9) Å, respectively (Fig. 2). The molecules of (I) are hydrogen bonded via N2—H2···N4 forming chains lying parallel to the a axis (details of hydrogen bonding geometry have been given in Table 1). The shortest distance between the centroids of pyridyl and triazole rings from two different molecules lying about inversion centers is 4.350 (3) Å.