Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039371/hg6276sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039371/hg6276Isup2.hkl |
CCDC reference: 296571
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (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
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.
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.
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.
C13H13N7S·H2O | F(000) = 664 |
Mr = 317.38 | Dx = 1.335 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yb c | Cell parameters from 2352 reflections |
a = 8.2900 (14) Å | θ = 2.8–25.0° |
b = 24.778 (5) Å | µ = 0.22 mm−1 |
c = 7.7083 (14) Å | T = 294 K |
β = 93.966 (3)° | Block, yellow |
V = 1579.6 (5) Å3 | 0.22 × 0.20 × 0.12 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 3234 independent reflections |
Radiation source: fine-focus sealed tube | 2039 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ϕ and ω scans | θmax = 26.4°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→8 |
Tmin = 0.952, Tmax = 0.974 | k = −31→26 |
8843 measured reflections | l = −9→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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H 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 parameters | Δρmax = 0.20 e Å−3 |
4 restraints | Δρmin = −0.16 e Å−3 |
C13H13N7S·H2O | V = 1579.6 (5) Å3 |
Mr = 317.38 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.2900 (14) Å | µ = 0.22 mm−1 |
b = 24.778 (5) Å | T = 294 K |
c = 7.7083 (14) Å | 0.22 × 0.20 × 0.12 mm |
β = 93.966 (3)° |
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 = 0.974 | Rint = 0.031 |
8843 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 4 restraints |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.20 e Å−3 |
3234 reflections | Δρmin = −0.16 e Å−3 |
212 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 | 0.47939 (8) | 0.42502 (2) | 1.50732 (7) | 0.0562 (2) | |
N1 | 0.3880 (2) | 0.42173 (7) | 1.0622 (2) | 0.0411 (4) | |
N2 | 0.47892 (19) | 0.38595 (6) | 1.1688 (2) | 0.0368 (4) | |
N3 | 0.6299 (2) | 0.31307 (7) | 1.2044 (2) | 0.0429 (4) | |
N4 | 0.6162 (2) | 0.33966 (7) | 1.3589 (2) | 0.0434 (4) | |
H4A | 0.666 (2) | 0.3255 (8) | 1.4563 (19) | 0.055 (7)* | |
N5 | 0.3512 (2) | 0.30957 (7) | 0.8688 (2) | 0.0442 (4) | |
N6 | 0.2936 (3) | 0.26787 (9) | 0.9591 (3) | 0.0806 (7) | |
N7 | 0.1000 (2) | 0.30189 (8) | 0.7734 (2) | 0.0580 (5) | |
C1 | 0.3436 (2) | 0.46638 (8) | 1.1239 (3) | 0.0450 (5) | |
H1 | 0.3692 | 0.4746 | 1.2402 | 0.054* | |
C2 | 0.2523 (2) | 0.50479 (8) | 1.0122 (3) | 0.0446 (5) | |
C3 | 0.2269 (3) | 0.49771 (10) | 0.8344 (3) | 0.0604 (6) | |
H3 | 0.2684 | 0.4674 | 0.7819 | 0.073* | |
C4 | 0.1399 (3) | 0.53561 (12) | 0.7344 (4) | 0.0733 (8) | |
H4 | 0.1243 | 0.5304 | 0.6149 | 0.088* | |
C5 | 0.0760 (3) | 0.58082 (11) | 0.8081 (5) | 0.0715 (8) | |
C6 | −0.0211 (4) | 0.62108 (14) | 0.6946 (5) | 0.1150 (14) | |
H6A | −0.0066 | 0.6566 | 0.7425 | 0.172* | |
H6B | −0.1336 | 0.6116 | 0.6904 | 0.172* | |
H6C | 0.0155 | 0.6204 | 0.5791 | 0.172* | |
C7 | 0.1041 (3) | 0.58815 (11) | 0.9827 (5) | 0.0761 (8) | |
H7 | 0.0642 | 0.6189 | 1.0342 | 0.091* | |
C8 | 0.1909 (3) | 0.55084 (10) | 1.0853 (4) | 0.0631 (7) | |
H8 | 0.2080 | 0.5568 | 1.2042 | 0.076* | |
C9 | 0.5245 (2) | 0.38431 (8) | 1.3460 (3) | 0.0393 (5) | |
C10 | 0.5447 (2) | 0.34204 (8) | 1.0914 (2) | 0.0389 (5) | |
C11 | 0.5168 (3) | 0.32806 (9) | 0.9048 (3) | 0.0475 (5) | |
H11A | 0.5362 | 0.3595 | 0.8341 | 0.057* | |
H11B | 0.5913 | 0.2999 | 0.8752 | 0.057* | |
C12 | 0.2353 (3) | 0.32870 (9) | 0.7616 (3) | 0.0523 (6) | |
H12 | 0.2474 | 0.3576 | 0.6867 | 0.063* | |
C13 | 0.1429 (4) | 0.26534 (11) | 0.8958 (3) | 0.0771 (9) | |
H13 | 0.0707 | 0.2399 | 0.9335 | 0.093* | |
O1 | 0.7877 (2) | 0.28744 (7) | 0.6178 (2) | 0.0667 (5) | |
H1A | 0.752 (3) | 0.2565 (6) | 0.648 (3) | 0.074 (9)* | |
H1B | 0.8821 (17) | 0.2948 (9) | 0.664 (3) | 0.085 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0817 (5) | 0.0467 (3) | 0.0399 (3) | 0.0009 (3) | 0.0018 (3) | −0.0047 (3) |
N1 | 0.0428 (10) | 0.0387 (10) | 0.0413 (9) | 0.0039 (8) | −0.0018 (8) | 0.0078 (8) |
N2 | 0.0376 (9) | 0.0357 (9) | 0.0364 (9) | 0.0010 (7) | −0.0030 (7) | 0.0033 (7) |
N3 | 0.0434 (10) | 0.0414 (10) | 0.0431 (10) | 0.0033 (8) | −0.0028 (8) | −0.0017 (8) |
N4 | 0.0487 (11) | 0.0411 (10) | 0.0388 (10) | 0.0013 (9) | −0.0080 (8) | 0.0029 (8) |
N5 | 0.0548 (11) | 0.0418 (10) | 0.0349 (9) | −0.0034 (9) | −0.0034 (8) | −0.0010 (8) |
N6 | 0.0928 (17) | 0.0708 (15) | 0.0738 (15) | −0.0306 (13) | −0.0267 (13) | 0.0299 (12) |
N7 | 0.0580 (13) | 0.0607 (13) | 0.0537 (12) | −0.0114 (11) | −0.0081 (10) | −0.0025 (10) |
C1 | 0.0497 (13) | 0.0417 (12) | 0.0434 (12) | 0.0015 (10) | 0.0017 (10) | 0.0052 (10) |
C2 | 0.0421 (13) | 0.0402 (12) | 0.0516 (13) | −0.0007 (10) | 0.0034 (10) | 0.0108 (10) |
C3 | 0.0642 (16) | 0.0568 (15) | 0.0595 (15) | 0.0042 (13) | −0.0011 (12) | 0.0127 (12) |
C4 | 0.0688 (18) | 0.082 (2) | 0.0671 (17) | −0.0097 (16) | −0.0118 (14) | 0.0317 (16) |
C5 | 0.0408 (14) | 0.0612 (18) | 0.111 (2) | −0.0021 (13) | −0.0024 (15) | 0.0424 (17) |
C6 | 0.065 (2) | 0.103 (3) | 0.174 (3) | 0.0048 (18) | −0.016 (2) | 0.083 (3) |
C7 | 0.0621 (17) | 0.0490 (16) | 0.119 (3) | 0.0166 (13) | 0.0162 (17) | 0.0199 (16) |
C8 | 0.0652 (16) | 0.0519 (15) | 0.0729 (17) | 0.0104 (13) | 0.0110 (13) | 0.0086 (13) |
C9 | 0.0399 (12) | 0.0373 (11) | 0.0400 (11) | −0.0070 (9) | −0.0022 (9) | 0.0042 (9) |
C10 | 0.0350 (11) | 0.0410 (12) | 0.0400 (11) | 0.0004 (9) | −0.0021 (9) | 0.0003 (9) |
C11 | 0.0453 (13) | 0.0556 (14) | 0.0417 (12) | 0.0058 (11) | 0.0037 (10) | −0.0042 (10) |
C12 | 0.0580 (15) | 0.0502 (13) | 0.0474 (13) | −0.0049 (12) | −0.0063 (11) | 0.0071 (11) |
C13 | 0.089 (2) | 0.078 (2) | 0.0616 (17) | −0.0409 (17) | −0.0145 (15) | 0.0138 (15) |
O1 | 0.0543 (11) | 0.0655 (12) | 0.0772 (12) | −0.0099 (9) | −0.0183 (10) | 0.0297 (10) |
S1—C9 | 1.664 (2) | C3—C4 | 1.386 (3) |
N1—C1 | 1.269 (3) | C3—H3 | 0.9300 |
N1—N2 | 1.394 (2) | C4—C5 | 1.379 (4) |
N2—C10 | 1.372 (2) | C4—H4 | 0.9300 |
N2—C9 | 1.392 (2) | C5—C7 | 1.362 (4) |
N3—C10 | 1.299 (2) | C5—C6 | 1.520 (3) |
N3—N4 | 1.372 (2) | C6—H6A | 0.9600 |
N4—C9 | 1.342 (3) | C6—H6B | 0.9600 |
N4—H4A | 0.902 (9) | C6—H6C | 0.9600 |
N5—C12 | 1.312 (3) | C7—C8 | 1.385 (4) |
N5—N6 | 1.351 (3) | C7—H7 | 0.9300 |
N5—C11 | 1.456 (3) | C8—H8 | 0.9300 |
N6—C13 | 1.311 (3) | C10—C11 | 1.482 (3) |
N7—C12 | 1.312 (3) | C11—H11A | 0.9700 |
N7—C13 | 1.338 (3) | C11—H11B | 0.9700 |
C1—C2 | 1.459 (3) | C12—H12 | 0.9300 |
C1—H1 | 0.9300 | C13—H13 | 0.9300 |
C2—C3 | 1.383 (3) | O1—H1A | 0.860 (9) |
C2—C8 | 1.385 (3) | O1—H1B | 0.857 (9) |
C1—N1—N2 | 119.51 (17) | H6A—C6—H6B | 109.5 |
C10—N2—C9 | 108.34 (15) | C5—C6—H6C | 109.5 |
C10—N2—N1 | 117.57 (15) | H6A—C6—H6C | 109.5 |
C9—N2—N1 | 134.08 (16) | H6B—C6—H6C | 109.5 |
C10—N3—N4 | 104.05 (16) | C5—C7—C8 | 121.4 (3) |
C9—N4—N3 | 114.34 (16) | C5—C7—H7 | 119.3 |
C9—N4—H4A | 127.3 (14) | C8—C7—H7 | 119.3 |
N3—N4—H4A | 118.3 (14) | C7—C8—C2 | 120.6 (3) |
C12—N5—N6 | 109.35 (19) | C7—C8—H8 | 119.7 |
C12—N5—C11 | 130.26 (19) | C2—C8—H8 | 119.7 |
N6—N5—C11 | 120.31 (18) | N4—C9—N2 | 102.15 (16) |
C13—N6—N5 | 101.9 (2) | N4—C9—S1 | 126.85 (15) |
C12—N7—C13 | 101.8 (2) | N2—C9—S1 | 130.99 (15) |
N1—C1—C2 | 120.0 (2) | N3—C10—N2 | 111.12 (17) |
N1—C1—H1 | 120.0 | N3—C10—C11 | 124.28 (19) |
C2—C1—H1 | 120.0 | N2—C10—C11 | 124.56 (17) |
C3—C2—C8 | 118.2 (2) | N5—C11—C10 | 109.92 (17) |
C3—C2—C1 | 122.6 (2) | N5—C11—H11A | 109.7 |
C8—C2—C1 | 119.2 (2) | C10—C11—H11A | 109.7 |
C2—C3—C4 | 120.2 (3) | N5—C11—H11B | 109.7 |
C2—C3—H3 | 119.9 | C10—C11—H11B | 109.7 |
C4—C3—H3 | 119.9 | H11A—C11—H11B | 108.2 |
C5—C4—C3 | 121.4 (3) | N5—C12—N7 | 111.4 (2) |
C5—C4—H4 | 119.3 | N5—C12—H12 | 124.3 |
C3—C4—H4 | 119.3 | N7—C12—H12 | 124.3 |
C7—C5—C4 | 118.1 (2) | N6—C13—N7 | 115.4 (2) |
C7—C5—C6 | 121.9 (3) | N6—C13—H13 | 122.3 |
C4—C5—C6 | 119.9 (3) | N7—C13—H13 | 122.3 |
C5—C6—H6A | 109.5 | H1A—O1—H1B | 113.3 (15) |
C5—C6—H6B | 109.5 | ||
C1—N1—N2—C10 | −170.49 (18) | C10—N2—C9—N4 | 0.9 (2) |
C1—N1—N2—C9 | 8.1 (3) | N1—N2—C9—N4 | −177.83 (19) |
C10—N3—N4—C9 | 0.2 (2) | C10—N2—C9—S1 | −178.27 (16) |
C12—N5—N6—C13 | 0.2 (3) | N1—N2—C9—S1 | 3.0 (3) |
C11—N5—N6—C13 | 177.3 (2) | N4—N3—C10—N2 | 0.4 (2) |
N2—N1—C1—C2 | 178.25 (17) | N4—N3—C10—C11 | −177.16 (19) |
N1—C1—C2—C3 | −7.7 (3) | C9—N2—C10—N3 | −0.8 (2) |
N1—C1—C2—C8 | 173.6 (2) | N1—N2—C10—N3 | 178.13 (16) |
C8—C2—C3—C4 | −1.0 (3) | C9—N2—C10—C11 | 176.72 (18) |
C1—C2—C3—C4 | −179.7 (2) | N1—N2—C10—C11 | −4.3 (3) |
C2—C3—C4—C5 | −0.4 (4) | C12—N5—C11—C10 | 120.6 (2) |
C3—C4—C5—C7 | 1.7 (4) | N6—N5—C11—C10 | −55.8 (3) |
C3—C4—C5—C6 | −179.0 (2) | N3—C10—C11—N5 | 106.7 (2) |
C4—C5—C7—C8 | −1.6 (4) | N2—C10—C11—N5 | −70.5 (3) |
C6—C5—C7—C8 | 179.1 (2) | N6—N5—C12—N7 | −0.2 (3) |
C5—C7—C8—C2 | 0.2 (4) | C11—N5—C12—N7 | −176.94 (19) |
C3—C2—C8—C7 | 1.1 (4) | C13—N7—C12—N5 | 0.2 (3) |
C1—C2—C8—C7 | 179.8 (2) | N5—N6—C13—N7 | −0.1 (3) |
N3—N4—C9—N2 | −0.7 (2) | C12—N7—C13—N6 | 0.0 (3) |
N3—N4—C9—S1 | 178.50 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N3i | 0.86 (2) | 2.06 (3) | 2.912 (3) | 171 |
O1—H1B···N7ii | 0.86 (2) | 1.95 (3) | 2.800 (2) | 173 |
N4—H4A···O1iii | 0.90 (2) | 1.81 (2) | 2.699 (2) | 167 |
C1—H1···S1 | 0.93 | 2.51 | 3.255 (2) | 137 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x+1, y, z; (iii) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C13H13N7S·H2O |
Mr | 317.38 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 8.2900 (14), 24.778 (5), 7.7083 (14) |
β (°) | 93.966 (3) |
V (Å3) | 1579.6 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.22 |
Crystal size (mm) | 0.22 × 0.20 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.952, 0.974 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8843, 3234, 2039 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.113, 1.02 |
No. of reflections | 3234 |
No. of parameters | 212 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.16 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL.
S1—C9 | 1.664 (2) | N3—N4 | 1.372 (2) |
N1—C1 | 1.269 (3) | N5—N6 | 1.351 (3) |
N1—N2 | 1.394 (2) | ||
C1—N1—N2 | 119.51 (17) | C10—N3—N4 | 104.05 (16) |
C10—N2—C9 | 108.34 (15) | N5—C11—C10 | 109.92 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N3i | 0.860 (17) | 2.06 (3) | 2.912 (3) | 171 |
O1—H1B···N7ii | 0.857 (17) | 1.95 (3) | 2.800 (2) | 173 |
N4—H4A···O1iii | 0.902 (16) | 1.81 (2) | 2.699 (2) | 167 |
C1—H1···S1 | 0.93 | 2.51000 | 3.255 (2) | 137 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x+1, y, z; (iii) x, y, z+1. |
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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 S═C 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 π–π stacking interactions. The π–π 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.