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In the title compound, C13H15N7OS, the dihedral angles made by the plane of the thione-substituted triazole ring with the planes of the other triazole ring and the benzene ring are 88.69 (3) and 2.94 (2)°, respectively. Inter- and intra­molecular hydrogen-bond and π–π stacking inter­actions stabilize the structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039371/hg6276sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039371/hg6276Isup2.hkl
Contains datablock I

CCDC reference: 296571

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.041
  • wR factor = 0.113
  • Data-to-parameter ratio = 15.3

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.96 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.18 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for N6 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N5 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C5
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Recently, compounds containing a 1H-1,2,4-triazole group have attracted much interest because compounds containing this ring system are well known as efficient fungicides in pesticides and they exhibit good plant-growth regulatory activity for a wide variety of crops (Xu et al., 2002). In addition, amine- and thione-substituted triazoles have been studied as anti-inflammatory and antimicrobial agents (Eweiss et al.,1986; Awad et al., 1991). In a search for new triazole compounds with better biological activity, the title compound, (I), was synthesized. We report here the crystal structure of (I).

Compound (I) crystallizes as a monohydrate. The bond lengths and angles are generally normal in the thione-substituted triazole ring and the other triazole ring (Xu et al., 2005). The molecule exists in the thione tautomeric form, with an SC distance of 1.664 (2) Å, which indicates substantial double-bond character for this bond (Allen et al., 1987). The planes C11/C12/N5/N6/N7 [should this include C13?] and C1–C8 make angles of 88.69 (3) and 2.94 (2)°, respectively, with the thione-substituted triazole plane C9/C10/N2–N4/S1. The crystal structure of (I) is stabilized by weak intra- and intermolecular hydrogen bonds and ππ stacking interactions. The ππ stacking interactions involve the thione-substituted triazole ring (C9/C10/N2–N4) R1 and the benzene ring (C2–C5/C7/C8) R2. The distance between the centroids of rings R1 and R2 (at 1 − x, −y, 1 − z) is 3.668 (2) Å.

Experimental top

A mixture of 4-amino-3-(1,2,4-triazol-1-yl)-1H-1,2,4-triazole-5(4H)-thione (0.02 mol) and 4-methylbenzaldehyde (0.02 mol) was refluxed at 391 K for 20 min in glacial acetic acid. The mixture was then filtered and crystallized from ethanol to afford the compound 5-[(1H-1,2,4-triazol-1-yl)methyl]-4-(4-methylbenzylideneamino)-2H-1,2,4-triazole-3(4H)-thione (5.32 g, yield 89%). Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

Refinement top

All C-bound H atoms were placed in calculated positions, with C—H = 0.93–0.97 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) values of 1.2Ueq(C) for the aryl and methylene H atoms, and 1.5Ueq(C) for the methyl H atoms. The position and isotropic displacement parameters of the N-bound and O-bound H atoms were refined freely.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. View of (I), with displacement ellipsoids for non-H atoms drawn at the 40% probability level.
[Figure 2] Fig. 2. A packing diagram of the molecule of the title compound, viewed down the c axis. Hydrogen bonds are shown as dashed lines.
4-(4-Methylbenzylideneamino)-3-[(1H-1,2,4-triazol-1-yl)methyl]-1H-1,2,4- triazole-5(4H)-thione monohydrate top
Crystal data top
C13H13N7S·H2OF(000) = 664
Mr = 317.38Dx = 1.335 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb cCell parameters from 2352 reflections
a = 8.2900 (14) Åθ = 2.8–25.0°
b = 24.778 (5) ŵ = 0.22 mm1
c = 7.7083 (14) ÅT = 294 K
β = 93.966 (3)°Block, yellow
V = 1579.6 (5) Å30.22 × 0.20 × 0.12 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
3234 independent reflections
Radiation source: fine-focus sealed tube2039 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ϕ and ω scansθmax = 26.4°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 108
Tmin = 0.952, Tmax = 0.974k = 3126
8843 measured reflectionsl = 98
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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0501P)2 + 0.2737P]
where P = (Fo2 + 2Fc2)/3
3234 reflections(Δ/σ)max = 0.004
212 parametersΔρmax = 0.20 e Å3
4 restraintsΔρmin = 0.16 e Å3
Crystal data top
C13H13N7S·H2OV = 1579.6 (5) Å3
Mr = 317.38Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.2900 (14) ŵ = 0.22 mm1
b = 24.778 (5) ÅT = 294 K
c = 7.7083 (14) Å0.22 × 0.20 × 0.12 mm
β = 93.966 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3234 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2039 reflections with I > 2σ(I)
Tmin = 0.952, Tmax = 0.974Rint = 0.031
8843 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0414 restraints
wR(F2) = 0.113H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.20 e Å3
3234 reflectionsΔρmin = 0.16 e Å3
212 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
S10.47939 (8)0.42502 (2)1.50732 (7)0.0562 (2)
N10.3880 (2)0.42173 (7)1.0622 (2)0.0411 (4)
N20.47892 (19)0.38595 (6)1.1688 (2)0.0368 (4)
N30.6299 (2)0.31307 (7)1.2044 (2)0.0429 (4)
N40.6162 (2)0.33966 (7)1.3589 (2)0.0434 (4)
H4A0.666 (2)0.3255 (8)1.4563 (19)0.055 (7)*
N50.3512 (2)0.30957 (7)0.8688 (2)0.0442 (4)
N60.2936 (3)0.26787 (9)0.9591 (3)0.0806 (7)
N70.1000 (2)0.30189 (8)0.7734 (2)0.0580 (5)
C10.3436 (2)0.46638 (8)1.1239 (3)0.0450 (5)
H10.36920.47461.24020.054*
C20.2523 (2)0.50479 (8)1.0122 (3)0.0446 (5)
C30.2269 (3)0.49771 (10)0.8344 (3)0.0604 (6)
H30.26840.46740.78190.073*
C40.1399 (3)0.53561 (12)0.7344 (4)0.0733 (8)
H40.12430.53040.61490.088*
C50.0760 (3)0.58082 (11)0.8081 (5)0.0715 (8)
C60.0211 (4)0.62108 (14)0.6946 (5)0.1150 (14)
H6A0.00660.65660.74250.172*
H6B0.13360.61160.69040.172*
H6C0.01550.62040.57910.172*
C70.1041 (3)0.58815 (11)0.9827 (5)0.0761 (8)
H70.06420.61891.03420.091*
C80.1909 (3)0.55084 (10)1.0853 (4)0.0631 (7)
H80.20800.55681.20420.076*
C90.5245 (2)0.38431 (8)1.3460 (3)0.0393 (5)
C100.5447 (2)0.34204 (8)1.0914 (2)0.0389 (5)
C110.5168 (3)0.32806 (9)0.9048 (3)0.0475 (5)
H11A0.53620.35950.83410.057*
H11B0.59130.29990.87520.057*
C120.2353 (3)0.32870 (9)0.7616 (3)0.0523 (6)
H120.24740.35760.68670.063*
C130.1429 (4)0.26534 (11)0.8958 (3)0.0771 (9)
H130.07070.23990.93350.093*
O10.7877 (2)0.28744 (7)0.6178 (2)0.0667 (5)
H1A0.752 (3)0.2565 (6)0.648 (3)0.074 (9)*
H1B0.8821 (17)0.2948 (9)0.664 (3)0.085 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0817 (5)0.0467 (3)0.0399 (3)0.0009 (3)0.0018 (3)0.0047 (3)
N10.0428 (10)0.0387 (10)0.0413 (9)0.0039 (8)0.0018 (8)0.0078 (8)
N20.0376 (9)0.0357 (9)0.0364 (9)0.0010 (7)0.0030 (7)0.0033 (7)
N30.0434 (10)0.0414 (10)0.0431 (10)0.0033 (8)0.0028 (8)0.0017 (8)
N40.0487 (11)0.0411 (10)0.0388 (10)0.0013 (9)0.0080 (8)0.0029 (8)
N50.0548 (11)0.0418 (10)0.0349 (9)0.0034 (9)0.0034 (8)0.0010 (8)
N60.0928 (17)0.0708 (15)0.0738 (15)0.0306 (13)0.0267 (13)0.0299 (12)
N70.0580 (13)0.0607 (13)0.0537 (12)0.0114 (11)0.0081 (10)0.0025 (10)
C10.0497 (13)0.0417 (12)0.0434 (12)0.0015 (10)0.0017 (10)0.0052 (10)
C20.0421 (13)0.0402 (12)0.0516 (13)0.0007 (10)0.0034 (10)0.0108 (10)
C30.0642 (16)0.0568 (15)0.0595 (15)0.0042 (13)0.0011 (12)0.0127 (12)
C40.0688 (18)0.082 (2)0.0671 (17)0.0097 (16)0.0118 (14)0.0317 (16)
C50.0408 (14)0.0612 (18)0.111 (2)0.0021 (13)0.0024 (15)0.0424 (17)
C60.065 (2)0.103 (3)0.174 (3)0.0048 (18)0.016 (2)0.083 (3)
C70.0621 (17)0.0490 (16)0.119 (3)0.0166 (13)0.0162 (17)0.0199 (16)
C80.0652 (16)0.0519 (15)0.0729 (17)0.0104 (13)0.0110 (13)0.0086 (13)
C90.0399 (12)0.0373 (11)0.0400 (11)0.0070 (9)0.0022 (9)0.0042 (9)
C100.0350 (11)0.0410 (12)0.0400 (11)0.0004 (9)0.0021 (9)0.0003 (9)
C110.0453 (13)0.0556 (14)0.0417 (12)0.0058 (11)0.0037 (10)0.0042 (10)
C120.0580 (15)0.0502 (13)0.0474 (13)0.0049 (12)0.0063 (11)0.0071 (11)
C130.089 (2)0.078 (2)0.0616 (17)0.0409 (17)0.0145 (15)0.0138 (15)
O10.0543 (11)0.0655 (12)0.0772 (12)0.0099 (9)0.0183 (10)0.0297 (10)
Geometric parameters (Å, º) top
S1—C91.664 (2)C3—C41.386 (3)
N1—C11.269 (3)C3—H30.9300
N1—N21.394 (2)C4—C51.379 (4)
N2—C101.372 (2)C4—H40.9300
N2—C91.392 (2)C5—C71.362 (4)
N3—C101.299 (2)C5—C61.520 (3)
N3—N41.372 (2)C6—H6A0.9600
N4—C91.342 (3)C6—H6B0.9600
N4—H4A0.902 (9)C6—H6C0.9600
N5—C121.312 (3)C7—C81.385 (4)
N5—N61.351 (3)C7—H70.9300
N5—C111.456 (3)C8—H80.9300
N6—C131.311 (3)C10—C111.482 (3)
N7—C121.312 (3)C11—H11A0.9700
N7—C131.338 (3)C11—H11B0.9700
C1—C21.459 (3)C12—H120.9300
C1—H10.9300C13—H130.9300
C2—C31.383 (3)O1—H1A0.860 (9)
C2—C81.385 (3)O1—H1B0.857 (9)
C1—N1—N2119.51 (17)H6A—C6—H6B109.5
C10—N2—C9108.34 (15)C5—C6—H6C109.5
C10—N2—N1117.57 (15)H6A—C6—H6C109.5
C9—N2—N1134.08 (16)H6B—C6—H6C109.5
C10—N3—N4104.05 (16)C5—C7—C8121.4 (3)
C9—N4—N3114.34 (16)C5—C7—H7119.3
C9—N4—H4A127.3 (14)C8—C7—H7119.3
N3—N4—H4A118.3 (14)C7—C8—C2120.6 (3)
C12—N5—N6109.35 (19)C7—C8—H8119.7
C12—N5—C11130.26 (19)C2—C8—H8119.7
N6—N5—C11120.31 (18)N4—C9—N2102.15 (16)
C13—N6—N5101.9 (2)N4—C9—S1126.85 (15)
C12—N7—C13101.8 (2)N2—C9—S1130.99 (15)
N1—C1—C2120.0 (2)N3—C10—N2111.12 (17)
N1—C1—H1120.0N3—C10—C11124.28 (19)
C2—C1—H1120.0N2—C10—C11124.56 (17)
C3—C2—C8118.2 (2)N5—C11—C10109.92 (17)
C3—C2—C1122.6 (2)N5—C11—H11A109.7
C8—C2—C1119.2 (2)C10—C11—H11A109.7
C2—C3—C4120.2 (3)N5—C11—H11B109.7
C2—C3—H3119.9C10—C11—H11B109.7
C4—C3—H3119.9H11A—C11—H11B108.2
C5—C4—C3121.4 (3)N5—C12—N7111.4 (2)
C5—C4—H4119.3N5—C12—H12124.3
C3—C4—H4119.3N7—C12—H12124.3
C7—C5—C4118.1 (2)N6—C13—N7115.4 (2)
C7—C5—C6121.9 (3)N6—C13—H13122.3
C4—C5—C6119.9 (3)N7—C13—H13122.3
C5—C6—H6A109.5H1A—O1—H1B113.3 (15)
C5—C6—H6B109.5
C1—N1—N2—C10170.49 (18)C10—N2—C9—N40.9 (2)
C1—N1—N2—C98.1 (3)N1—N2—C9—N4177.83 (19)
C10—N3—N4—C90.2 (2)C10—N2—C9—S1178.27 (16)
C12—N5—N6—C130.2 (3)N1—N2—C9—S13.0 (3)
C11—N5—N6—C13177.3 (2)N4—N3—C10—N20.4 (2)
N2—N1—C1—C2178.25 (17)N4—N3—C10—C11177.16 (19)
N1—C1—C2—C37.7 (3)C9—N2—C10—N30.8 (2)
N1—C1—C2—C8173.6 (2)N1—N2—C10—N3178.13 (16)
C8—C2—C3—C41.0 (3)C9—N2—C10—C11176.72 (18)
C1—C2—C3—C4179.7 (2)N1—N2—C10—C114.3 (3)
C2—C3—C4—C50.4 (4)C12—N5—C11—C10120.6 (2)
C3—C4—C5—C71.7 (4)N6—N5—C11—C1055.8 (3)
C3—C4—C5—C6179.0 (2)N3—C10—C11—N5106.7 (2)
C4—C5—C7—C81.6 (4)N2—C10—C11—N570.5 (3)
C6—C5—C7—C8179.1 (2)N6—N5—C12—N70.2 (3)
C5—C7—C8—C20.2 (4)C11—N5—C12—N7176.94 (19)
C3—C2—C8—C71.1 (4)C13—N7—C12—N50.2 (3)
C1—C2—C8—C7179.8 (2)N5—N6—C13—N70.1 (3)
N3—N4—C9—N20.7 (2)C12—N7—C13—N60.0 (3)
N3—N4—C9—S1178.50 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N3i0.86 (2)2.06 (3)2.912 (3)171
O1—H1B···N7ii0.86 (2)1.95 (3)2.800 (2)173
N4—H4A···O1iii0.90 (2)1.81 (2)2.699 (2)167
C1—H1···S10.932.513.255 (2)137
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x+1, y, z; (iii) x, y, z+1.

Experimental details

Crystal data
Chemical formulaC13H13N7S·H2O
Mr317.38
Crystal system, space groupMonoclinic, P21/c
Temperature (K)294
a, b, c (Å)8.2900 (14), 24.778 (5), 7.7083 (14)
β (°) 93.966 (3)
V3)1579.6 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.22
Crystal size (mm)0.22 × 0.20 × 0.12
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.952, 0.974
No. of measured, independent and
observed [I > 2σ(I)] reflections
8843, 3234, 2039
Rint0.031
(sin θ/λ)max1)0.626
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.113, 1.02
No. of reflections3234
No. of parameters212
No. of restraints4
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.20, 0.16

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL.

Selected geometric parameters (Å, º) top
S1—C91.664 (2)N3—N41.372 (2)
N1—C11.269 (3)N5—N61.351 (3)
N1—N21.394 (2)
C1—N1—N2119.51 (17)C10—N3—N4104.05 (16)
C10—N2—C9108.34 (15)N5—C11—C10109.92 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N3i0.860 (17)2.06 (3)2.912 (3)171
O1—H1B···N7ii0.857 (17)1.95 (3)2.800 (2)173
N4—H4A···O1iii0.902 (16)1.81 (2)2.699 (2)167
C1—H1···S10.932.510003.255 (2)137
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x+1, y, z; (iii) x, y, z+1.
 

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