Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039954/cv6615sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039954/cv6615Isup2.hkl |
CCDC reference: 296549
4-Amino-5-mercapto-3-propyl-1,2,4-triazole was prepared by the reaction of the propanoic acid and thiocarbohydrazide, following the literature method of Francesco et al. (1997). To a solution of 4-amino-5-mercapto-3-propyl-1,2,4-trizole (0.001 mol) in absolute ethanol was added 2-bromo-4-fluoroacetophenone (0.001 mol). The mixture was refluxed for 7 h. The solid obtained on cooling was filtered, washed with cold water, dried and recrystallized from ethanol to give compound (I). The purified product was dissolved in 95% ethanol and kept at room temperature for 5 d and colourless single crystals of (I) were formed (m.p. 454–455 K). IR(KBr, cm−1): 3055, 3001 (Ar—H), 2922(CH2), 1610 (C═N), 1483, 1296 (N—N═C), 1176 (C—F), 834, 731(di- and trisubstituted benzene), 691 (C—S—C). 1H NMR (dimethylsulfoxide-d6, p.p.m.): 7.86–7.99 (q, 3H, Ar—H), 7.50–7.57 (t, 1H, Ar—H), 7.27–7.32 (t, 1H, Ar—H), 7.03–7.13 (q, 2H, Ar—H), 4.34 (s, 2H, CH2), 3.82 (s, 3H, OCH3). 13C NMR (dimethylsulfoxide-d6, p.p.m.): 162.70, 159.10, 152.94, 151.624, 141.93, 132.26, 129.70, 119.711, 118.31, 112.89, 105.47, 55.48, 25.95. Elemental analysis for C17H12F2N4OS: C 56.53, H 3.56, N 15.92%; calculated: C 56.92, H 3.38, N 15.69%.
All H atoms were positioned geometrically and allowed to ride on their parent atoms at distances of Csp2—H = 0.93 Å with Uiso=1.2Ueq(parent atom), and Csp3—H = 0.96 or 0.97 Å with Uiso=1.5Ueq(parent atom).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXLTL (Bruker, 2002); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular structure of (I), showing the atom-numbering scheme, with displacement ellipsoids drawn at the 30% probability level. |
C13H13FN4S | F(000) = 576 |
Mr = 276.33 | Dx = 1.399 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3328 reflections |
a = 12.5849 (9) Å | θ = 2.5–24.1° |
b = 14.5963 (10) Å | µ = 0.25 mm−1 |
c = 7.2955 (5) Å | T = 298 K |
β = 101.825 (1)° | Block, colourless |
V = 1311.69 (16) Å3 | 0.29 × 0.19 × 0.11 mm |
Z = 4 |
Bruker APEX area-detector diffractometer | 2374 independent reflections |
Radiation source: fine-focus sealed tube | 2180 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ϕ and ω scans | θmax = 25.2°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −15→15 |
Tmin = 0.931, Tmax = 0.968 | k = −17→17 |
12592 measured reflections | l = −8→8 |
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)] = 0.066 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.26 | w = 1/[σ2(Fo2) + (0.0522P)2 + 0.9704P] where P = (Fo2 + 2Fc2)/3 |
2374 reflections | (Δ/σ)max = 0.001 |
173 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C13H13FN4S | V = 1311.69 (16) Å3 |
Mr = 276.33 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.5849 (9) Å | µ = 0.25 mm−1 |
b = 14.5963 (10) Å | T = 298 K |
c = 7.2955 (5) Å | 0.29 × 0.19 × 0.11 mm |
β = 101.825 (1)° |
Bruker APEX area-detector diffractometer | 2374 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 2180 reflections with I > 2σ(I) |
Tmin = 0.931, Tmax = 0.968 | Rint = 0.030 |
12592 measured reflections |
R[F2 > 2σ(F2)] = 0.066 | 0 restraints |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.26 | Δρmax = 0.40 e Å−3 |
2374 reflections | Δρmin = −0.20 e Å−3 |
173 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 | 1.03917 (6) | 0.67104 (5) | 0.20809 (11) | 0.0429 (3) | |
F1 | 0.46490 (18) | 0.90948 (17) | 0.1253 (4) | 0.0898 (8) | |
N1 | 0.80754 (18) | 0.59551 (15) | 0.2170 (3) | 0.0346 (5) | |
N2 | 0.89568 (19) | 0.53717 (15) | 0.2284 (3) | 0.0352 (5) | |
N3 | 1.0630 (2) | 0.48661 (19) | 0.2756 (4) | 0.0472 (7) | |
N4 | 0.9934 (2) | 0.41426 (17) | 0.2994 (4) | 0.0473 (7) | |
C1 | 0.5501 (3) | 0.8528 (2) | 0.1267 (5) | 0.0512 (8) | |
C2 | 0.6476 (3) | 0.8893 (2) | 0.1116 (4) | 0.0476 (8) | |
H2 | 0.6557 | 0.9523 | 0.1005 | 0.057* | |
C3 | 0.7340 (2) | 0.83096 (19) | 0.1131 (4) | 0.0370 (6) | |
H3 | 0.8008 | 0.8550 | 0.1021 | 0.044* | |
C4 | 0.7228 (2) | 0.73691 (18) | 0.1308 (3) | 0.0315 (6) | |
C5 | 0.6212 (2) | 0.7027 (2) | 0.1452 (4) | 0.0411 (7) | |
H5 | 0.6118 | 0.6399 | 0.1564 | 0.049* | |
C6 | 0.5350 (2) | 0.7607 (2) | 0.1432 (5) | 0.0504 (8) | |
H6 | 0.4674 | 0.7376 | 0.1529 | 0.061* | |
C7 | 0.8156 (2) | 0.67395 (18) | 0.1404 (3) | 0.0317 (6) | |
C8 | 0.9110 (2) | 0.7009 (2) | 0.0573 (4) | 0.0376 (7) | |
H8A | 0.9090 | 0.7665 | 0.0352 | 0.045* | |
H8B | 0.9055 | 0.6705 | −0.0626 | 0.045* | |
C9 | 1.0020 (2) | 0.5582 (2) | 0.2341 (4) | 0.0368 (7) | |
C10 | 0.8949 (2) | 0.44609 (19) | 0.2739 (4) | 0.0392 (7) | |
C11 | 0.7956 (3) | 0.3943 (2) | 0.2857 (5) | 0.0501 (8) | |
H11A | 0.7449 | 0.4354 | 0.3276 | 0.060* | |
H11B | 0.8144 | 0.3467 | 0.3795 | 0.060* | |
C12 | 0.7393 (3) | 0.3503 (3) | 0.1025 (5) | 0.0623 (10) | |
H12A | 0.7902 | 0.3097 | 0.0600 | 0.075* | |
H12B | 0.6795 | 0.3133 | 0.1259 | 0.075* | |
C13 | 0.6963 (4) | 0.4171 (3) | −0.0510 (6) | 0.0844 (14) | |
H13A | 0.6422 | 0.4552 | −0.0139 | 0.127* | |
H13B | 0.6645 | 0.3842 | −0.1628 | 0.127* | |
H13C | 0.7547 | 0.4546 | −0.0747 | 0.127* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0359 (4) | 0.0454 (5) | 0.0470 (5) | −0.0034 (3) | 0.0078 (3) | −0.0009 (3) |
F1 | 0.0643 (14) | 0.0811 (16) | 0.131 (2) | 0.0371 (12) | 0.0364 (14) | 0.0173 (15) |
N1 | 0.0374 (13) | 0.0322 (12) | 0.0350 (12) | 0.0027 (10) | 0.0096 (10) | −0.0008 (10) |
N2 | 0.0411 (13) | 0.0318 (12) | 0.0338 (12) | 0.0036 (10) | 0.0099 (10) | 0.0005 (10) |
N3 | 0.0451 (15) | 0.0496 (16) | 0.0470 (15) | 0.0102 (13) | 0.0095 (12) | −0.0001 (12) |
N4 | 0.0567 (16) | 0.0411 (15) | 0.0447 (15) | 0.0116 (13) | 0.0117 (12) | 0.0010 (11) |
C1 | 0.0444 (18) | 0.055 (2) | 0.0542 (19) | 0.0199 (15) | 0.0102 (15) | 0.0038 (16) |
C2 | 0.056 (2) | 0.0369 (16) | 0.0508 (18) | 0.0080 (14) | 0.0125 (15) | 0.0038 (14) |
C3 | 0.0388 (15) | 0.0388 (15) | 0.0330 (14) | −0.0009 (13) | 0.0067 (12) | 0.0014 (12) |
C4 | 0.0355 (15) | 0.0341 (14) | 0.0243 (12) | 0.0004 (11) | 0.0046 (11) | −0.0007 (11) |
C5 | 0.0403 (17) | 0.0389 (16) | 0.0434 (16) | −0.0025 (13) | 0.0068 (13) | 0.0023 (13) |
C6 | 0.0325 (16) | 0.061 (2) | 0.058 (2) | −0.0012 (15) | 0.0102 (14) | 0.0018 (16) |
C7 | 0.0360 (14) | 0.0335 (14) | 0.0250 (13) | −0.0007 (12) | 0.0049 (11) | −0.0033 (11) |
C8 | 0.0408 (16) | 0.0397 (16) | 0.0343 (15) | 0.0046 (12) | 0.0122 (12) | 0.0051 (12) |
C9 | 0.0371 (15) | 0.0428 (17) | 0.0306 (14) | 0.0055 (13) | 0.0069 (12) | −0.0049 (12) |
C10 | 0.0524 (18) | 0.0325 (15) | 0.0337 (15) | 0.0075 (13) | 0.0112 (13) | 0.0004 (12) |
C11 | 0.065 (2) | 0.0358 (16) | 0.0542 (19) | 0.0044 (15) | 0.0219 (16) | 0.0094 (14) |
C12 | 0.066 (2) | 0.054 (2) | 0.068 (2) | −0.0142 (18) | 0.0162 (19) | 0.0026 (18) |
C13 | 0.087 (3) | 0.082 (3) | 0.074 (3) | −0.028 (2) | −0.008 (2) | 0.015 (2) |
S1—C9 | 1.733 (3) | C4—C7 | 1.477 (4) |
S1—C8 | 1.809 (3) | C5—C6 | 1.373 (4) |
F1—C1 | 1.353 (4) | C5—H5 | 0.9300 |
N1—C7 | 1.287 (3) | C6—H6 | 0.9300 |
N1—N2 | 1.387 (3) | C7—C8 | 1.504 (4) |
N2—C9 | 1.365 (4) | C8—H8A | 0.9700 |
N2—C10 | 1.371 (4) | C8—H8B | 0.9700 |
N3—C9 | 1.296 (4) | C10—C11 | 1.478 (4) |
N3—N4 | 1.406 (4) | C11—C12 | 1.520 (5) |
N4—C10 | 1.301 (4) | C11—H11A | 0.9700 |
C1—C2 | 1.362 (5) | C11—H11B | 0.9700 |
C1—C6 | 1.367 (5) | C12—C13 | 1.499 (5) |
C2—C3 | 1.379 (4) | C12—H12A | 0.9700 |
C2—H2 | 0.9300 | C12—H12B | 0.9700 |
C3—C4 | 1.389 (4) | C13—H13A | 0.9600 |
C3—H3 | 0.9300 | C13—H13B | 0.9600 |
C4—C5 | 1.396 (4) | C13—H13C | 0.9600 |
C9—S1—C8 | 93.92 (14) | C7—C8—H8A | 109.2 |
C7—N1—N2 | 116.0 (2) | S1—C8—H8A | 109.2 |
C9—N2—C10 | 105.5 (2) | C7—C8—H8B | 109.2 |
C9—N2—N1 | 129.1 (2) | S1—C8—H8B | 109.2 |
C10—N2—N1 | 124.4 (2) | H8A—C8—H8B | 107.9 |
C9—N3—N4 | 106.3 (2) | N3—C9—N2 | 110.8 (3) |
C10—N4—N3 | 108.3 (2) | N3—C9—S1 | 129.2 (2) |
F1—C1—C2 | 119.0 (3) | N2—C9—S1 | 119.7 (2) |
F1—C1—C6 | 118.5 (3) | N4—C10—N2 | 109.1 (3) |
C2—C1—C6 | 122.4 (3) | N4—C10—C11 | 127.0 (3) |
C1—C2—C3 | 118.6 (3) | N2—C10—C11 | 124.0 (3) |
C1—C2—H2 | 120.7 | C10—C11—C12 | 114.4 (3) |
C3—C2—H2 | 120.7 | C10—C11—H11A | 108.7 |
C2—C3—C4 | 121.1 (3) | C12—C11—H11A | 108.7 |
C2—C3—H3 | 119.5 | C10—C11—H11B | 108.7 |
C4—C3—H3 | 119.5 | C12—C11—H11B | 108.7 |
C3—C4—C5 | 118.2 (3) | H11A—C11—H11B | 107.6 |
C3—C4—C7 | 121.7 (2) | C13—C12—C11 | 114.5 (3) |
C5—C4—C7 | 120.1 (2) | C13—C12—H12A | 108.6 |
C6—C5—C4 | 120.9 (3) | C11—C12—H12A | 108.6 |
C6—C5—H5 | 119.6 | C13—C12—H12B | 108.6 |
C4—C5—H5 | 119.6 | C11—C12—H12B | 108.6 |
C1—C6—C5 | 118.8 (3) | H12A—C12—H12B | 107.6 |
C1—C6—H6 | 120.6 | C12—C13—H13A | 109.5 |
C5—C6—H6 | 120.6 | C12—C13—H13B | 109.5 |
N1—C7—C4 | 116.2 (2) | H13A—C13—H13B | 109.5 |
N1—C7—C8 | 123.2 (2) | C12—C13—H13C | 109.5 |
C4—C7—C8 | 120.5 (2) | H13A—C13—H13C | 109.5 |
C7—C8—S1 | 112.18 (19) | H13B—C13—H13C | 109.5 |
Experimental details
Crystal data | |
Chemical formula | C13H13FN4S |
Mr | 276.33 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 12.5849 (9), 14.5963 (10), 7.2955 (5) |
β (°) | 101.825 (1) |
V (Å3) | 1311.69 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.29 × 0.19 × 0.11 |
Data collection | |
Diffractometer | Bruker APEX area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.931, 0.968 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12592, 2374, 2180 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.600 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.066, 0.143, 1.26 |
No. of reflections | 2374 |
No. of parameters | 173 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.40, −0.20 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXLTL (Bruker, 2002), SHELXL97.
S1—C9 | 1.733 (3) | N2—C10 | 1.371 (4) |
S1—C8 | 1.809 (3) | N3—C9 | 1.296 (4) |
N1—C7 | 1.287 (3) | N3—N4 | 1.406 (4) |
N1—N2 | 1.387 (3) | N4—C10 | 1.301 (4) |
N2—C9 | 1.365 (4) | ||
C9—S1—C8 | 93.92 (14) | C10—N2—N1 | 124.4 (2) |
C7—N1—N2 | 116.0 (2) | C9—N3—N4 | 106.3 (2) |
C9—N2—C10 | 105.5 (2) | C10—N4—N3 | 108.3 (2) |
C9—N2—N1 | 129.1 (2) |
1,2,4-Triazoles fused with six-membered-ring systems have diverse applications in the fields of medicine, agriculture and industry. Commonly known systems are triazoles fused with pyridine, pyridazine, pyrimidine, pyrazines and triazines. A literature survey reveals that there are not many examples of triazoles fused with thiadiazines; these may exhibit antimicrobial (Feng et al.,1992) and diuretic (Mohan & Anjaneyulu, 1987) properties and act as photographic couplers (Holla et al., 2001). On the other hand, much attention has been paid to partially fluorinated heterocyclic compounds because of their unique chemical, physical and biological properties (Shaaban & Fuchigami, 2002). The development of efficient methods for selective fluorination of heterocycles is, therefore, of much importance. In this paper, we report the synthesis and crystal structure of the title compound, (I).
In (I), the six-membered thiadiazine ring N1/N2/C7/C8/C9/S1 (Fig. 1) is non-planar; atoms C8 and S1 deviate from the meaen plane by −0.398 (2) and 0.326 (1) Å, respectively. The S—C and C—N bond lengths (Table 1) are comparable with those observed in related compounds (Sert et al., 2003; Xiang et al., 2004). In the triazole rings, the C and N atoms are involved in the conjugated form, with the bond lengths and angles (Table 1) showing normal values (Allen et al., 1987; Jin et al., 2004). The mean plane of the thiadiazine ring makes dihedral angles of 10.2 (1) and 20.2 (2)°, respectively, with the triazole and benzene rings.