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The title compound, C13H13FN4S,was prepared by the reaction of 4-amino-5-mercapto-3-propyl-1,2,4-triazole and 2-bromo-4'-fluoroacetophenone. The bond lengths and angles show normal values. The thiadiazine ring is non-planar.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039954/cv6615sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039954/cv6615Isup2.hkl
Contains datablock I

CCDC reference: 296549

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.066
  • wR factor = 0.143
  • Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.68 Ratio
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 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 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

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.

Experimental top

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 (CN), 1483, 1296 (N—NC), 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%.

Refinement top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme, with displacement ellipsoids drawn at the 30% probability level.
6-(4-fluorophenyl)-3-propyl-7H-1,2,4-triazolo[3,4-b][1,3,4] thiadiazine top
Crystal data top
C13H13FN4SF(000) = 576
Mr = 276.33Dx = 1.399 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3328 reflections
a = 12.5849 (9) Åθ = 2.5–24.1°
b = 14.5963 (10) ŵ = 0.25 mm1
c = 7.2955 (5) ÅT = 298 K
β = 101.825 (1)°Block, colourless
V = 1311.69 (16) Å30.29 × 0.19 × 0.11 mm
Z = 4
Data collection top
Bruker APEX area-detector
diffractometer
2374 independent reflections
Radiation source: fine-focus sealed tube2180 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
ϕ and ω scansθmax = 25.2°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 1515
Tmin = 0.931, Tmax = 0.968k = 1717
12592 measured reflectionsl = 88
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.066Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143H-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 parametersΔρmax = 0.40 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C13H13FN4SV = 1311.69 (16) Å3
Mr = 276.33Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.5849 (9) ŵ = 0.25 mm1
b = 14.5963 (10) ÅT = 298 K
c = 7.2955 (5) Å0.29 × 0.19 × 0.11 mm
β = 101.825 (1)°
Data collection top
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 = 0.968Rint = 0.030
12592 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0660 restraints
wR(F2) = 0.143H-atom parameters constrained
S = 1.26Δρmax = 0.40 e Å3
2374 reflectionsΔρmin = 0.20 e Å3
173 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S11.03917 (6)0.67104 (5)0.20809 (11)0.0429 (3)
F10.46490 (18)0.90948 (17)0.1253 (4)0.0898 (8)
N10.80754 (18)0.59551 (15)0.2170 (3)0.0346 (5)
N20.89568 (19)0.53717 (15)0.2284 (3)0.0352 (5)
N31.0630 (2)0.48661 (19)0.2756 (4)0.0472 (7)
N40.9934 (2)0.41426 (17)0.2994 (4)0.0473 (7)
C10.5501 (3)0.8528 (2)0.1267 (5)0.0512 (8)
C20.6476 (3)0.8893 (2)0.1116 (4)0.0476 (8)
H20.65570.95230.10050.057*
C30.7340 (2)0.83096 (19)0.1131 (4)0.0370 (6)
H30.80080.85500.10210.044*
C40.7228 (2)0.73691 (18)0.1308 (3)0.0315 (6)
C50.6212 (2)0.7027 (2)0.1452 (4)0.0411 (7)
H50.61180.63990.15640.049*
C60.5350 (2)0.7607 (2)0.1432 (5)0.0504 (8)
H60.46740.73760.15290.061*
C70.8156 (2)0.67395 (18)0.1404 (3)0.0317 (6)
C80.9110 (2)0.7009 (2)0.0573 (4)0.0376 (7)
H8A0.90900.76650.03520.045*
H8B0.90550.67050.06260.045*
C91.0020 (2)0.5582 (2)0.2341 (4)0.0368 (7)
C100.8949 (2)0.44609 (19)0.2739 (4)0.0392 (7)
C110.7956 (3)0.3943 (2)0.2857 (5)0.0501 (8)
H11A0.74490.43540.32760.060*
H11B0.81440.34670.37950.060*
C120.7393 (3)0.3503 (3)0.1025 (5)0.0623 (10)
H12A0.79020.30970.06000.075*
H12B0.67950.31330.12590.075*
C130.6963 (4)0.4171 (3)0.0510 (6)0.0844 (14)
H13A0.64220.45520.01390.127*
H13B0.66450.38420.16280.127*
H13C0.75470.45460.07470.127*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0359 (4)0.0454 (5)0.0470 (5)0.0034 (3)0.0078 (3)0.0009 (3)
F10.0643 (14)0.0811 (16)0.131 (2)0.0371 (12)0.0364 (14)0.0173 (15)
N10.0374 (13)0.0322 (12)0.0350 (12)0.0027 (10)0.0096 (10)0.0008 (10)
N20.0411 (13)0.0318 (12)0.0338 (12)0.0036 (10)0.0099 (10)0.0005 (10)
N30.0451 (15)0.0496 (16)0.0470 (15)0.0102 (13)0.0095 (12)0.0001 (12)
N40.0567 (16)0.0411 (15)0.0447 (15)0.0116 (13)0.0117 (12)0.0010 (11)
C10.0444 (18)0.055 (2)0.0542 (19)0.0199 (15)0.0102 (15)0.0038 (16)
C20.056 (2)0.0369 (16)0.0508 (18)0.0080 (14)0.0125 (15)0.0038 (14)
C30.0388 (15)0.0388 (15)0.0330 (14)0.0009 (13)0.0067 (12)0.0014 (12)
C40.0355 (15)0.0341 (14)0.0243 (12)0.0004 (11)0.0046 (11)0.0007 (11)
C50.0403 (17)0.0389 (16)0.0434 (16)0.0025 (13)0.0068 (13)0.0023 (13)
C60.0325 (16)0.061 (2)0.058 (2)0.0012 (15)0.0102 (14)0.0018 (16)
C70.0360 (14)0.0335 (14)0.0250 (13)0.0007 (12)0.0049 (11)0.0033 (11)
C80.0408 (16)0.0397 (16)0.0343 (15)0.0046 (12)0.0122 (12)0.0051 (12)
C90.0371 (15)0.0428 (17)0.0306 (14)0.0055 (13)0.0069 (12)0.0049 (12)
C100.0524 (18)0.0325 (15)0.0337 (15)0.0075 (13)0.0112 (13)0.0004 (12)
C110.065 (2)0.0358 (16)0.0542 (19)0.0044 (15)0.0219 (16)0.0094 (14)
C120.066 (2)0.054 (2)0.068 (2)0.0142 (18)0.0162 (19)0.0026 (18)
C130.087 (3)0.082 (3)0.074 (3)0.028 (2)0.008 (2)0.015 (2)
Geometric parameters (Å, º) top
S1—C91.733 (3)C4—C71.477 (4)
S1—C81.809 (3)C5—C61.373 (4)
F1—C11.353 (4)C5—H50.9300
N1—C71.287 (3)C6—H60.9300
N1—N21.387 (3)C7—C81.504 (4)
N2—C91.365 (4)C8—H8A0.9700
N2—C101.371 (4)C8—H8B0.9700
N3—C91.296 (4)C10—C111.478 (4)
N3—N41.406 (4)C11—C121.520 (5)
N4—C101.301 (4)C11—H11A0.9700
C1—C21.362 (5)C11—H11B0.9700
C1—C61.367 (5)C12—C131.499 (5)
C2—C31.379 (4)C12—H12A0.9700
C2—H20.9300C12—H12B0.9700
C3—C41.389 (4)C13—H13A0.9600
C3—H30.9300C13—H13B0.9600
C4—C51.396 (4)C13—H13C0.9600
C9—S1—C893.92 (14)C7—C8—H8A109.2
C7—N1—N2116.0 (2)S1—C8—H8A109.2
C9—N2—C10105.5 (2)C7—C8—H8B109.2
C9—N2—N1129.1 (2)S1—C8—H8B109.2
C10—N2—N1124.4 (2)H8A—C8—H8B107.9
C9—N3—N4106.3 (2)N3—C9—N2110.8 (3)
C10—N4—N3108.3 (2)N3—C9—S1129.2 (2)
F1—C1—C2119.0 (3)N2—C9—S1119.7 (2)
F1—C1—C6118.5 (3)N4—C10—N2109.1 (3)
C2—C1—C6122.4 (3)N4—C10—C11127.0 (3)
C1—C2—C3118.6 (3)N2—C10—C11124.0 (3)
C1—C2—H2120.7C10—C11—C12114.4 (3)
C3—C2—H2120.7C10—C11—H11A108.7
C2—C3—C4121.1 (3)C12—C11—H11A108.7
C2—C3—H3119.5C10—C11—H11B108.7
C4—C3—H3119.5C12—C11—H11B108.7
C3—C4—C5118.2 (3)H11A—C11—H11B107.6
C3—C4—C7121.7 (2)C13—C12—C11114.5 (3)
C5—C4—C7120.1 (2)C13—C12—H12A108.6
C6—C5—C4120.9 (3)C11—C12—H12A108.6
C6—C5—H5119.6C13—C12—H12B108.6
C4—C5—H5119.6C11—C12—H12B108.6
C1—C6—C5118.8 (3)H12A—C12—H12B107.6
C1—C6—H6120.6C12—C13—H13A109.5
C5—C6—H6120.6C12—C13—H13B109.5
N1—C7—C4116.2 (2)H13A—C13—H13B109.5
N1—C7—C8123.2 (2)C12—C13—H13C109.5
C4—C7—C8120.5 (2)H13A—C13—H13C109.5
C7—C8—S1112.18 (19)H13B—C13—H13C109.5

Experimental details

Crystal data
Chemical formulaC13H13FN4S
Mr276.33
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)12.5849 (9), 14.5963 (10), 7.2955 (5)
β (°) 101.825 (1)
V3)1311.69 (16)
Z4
Radiation typeMo Kα
µ (mm1)0.25
Crystal size (mm)0.29 × 0.19 × 0.11
Data collection
DiffractometerBruker APEX area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2002)
Tmin, Tmax0.931, 0.968
No. of measured, independent and
observed [I > 2σ(I)] reflections
12592, 2374, 2180
Rint0.030
(sin θ/λ)max1)0.600
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.066, 0.143, 1.26
No. of reflections2374
No. of parameters173
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.40, 0.20

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXLTL (Bruker, 2002), SHELXL97.

Selected geometric parameters (Å, º) top
S1—C91.733 (3)N2—C101.371 (4)
S1—C81.809 (3)N3—C91.296 (4)
N1—C71.287 (3)N3—N41.406 (4)
N1—N21.387 (3)N4—C101.301 (4)
N2—C91.365 (4)
C9—S1—C893.92 (14)C10—N2—N1124.4 (2)
C7—N1—N2116.0 (2)C9—N3—N4106.3 (2)
C9—N2—C10105.5 (2)C10—N4—N3108.3 (2)
C9—N2—N1129.1 (2)
 

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