4-(2-Hydroxy­benzyl­ideneamino)-3-(1H-1,2,4-triazol-1-ylmeth­yl)-1H-1,2,4-triazole-5(4H)-thione

In the title compound, C₁₂H₁₁N₇OS, the dihedral angles made by the thione-substituted triazole ring with the other triazole ring and the benzene ring are 71.56 (2) and 47.89 (3)°, respectively. Inter- and intra­molcular hydrogen-bond inter­actions stabilize the structure.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.031
• wR factor = 0.087
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

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PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     -   C5      ..       5.68 su

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
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   1 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
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   0 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

Recently, compounds containing the 1H-1,2,4-triazole group have attracted much interest because compounds containing a triazole ring system are well known as effcient fungicides in pesticides, and have 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).

Bond lengths and angles of the triazole rings (Table 1) are in agreement with those in previous reports (Li et al., 2005; Xu et al., 2005). The molecule exists in the thione tautomeric form, with an S═ C distance of 1.6762 (15) Å, which indicates substantial double-bond character (Escobar-Valderrama et al., 1989). The planes C1–C3/N1/N2/N3 and C6–C12/N7/O1 make dihedral angles of 71.56 (2) and 47.89 (3)° with the thione-substituted triazole plane C4/C5/N4/N5/N6/S1. There are some intra- and intermolecular hydrogen-bond interactions which stabilize the crystal structure (Table 2).

S2. Experimental

A mixture of 4-amino-3-(1,2,4-triazol-1-yl)-1H-1,2,4-triazole-5(4H)-thione (0.02 mol) and 2-hydroxybenzaldehyde (0.02 mol) were refluxed at 391 K for 15–20 min in glacial acetic acid. The mixture was then filtered and crystallized from ethanol to afford the title compound (5.7 g, yield 95%). Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

S3. Refinement

H atoms bonded to C atoms were placed in calculated positions and constrained to ride on their parent atoms (C—H = 0.93–0.96 Å) with U_iso(H) = 1.2U_eq(C). The positions and isotropic displacement parameters of the H atoms attached to the N and O atoms were refined freely.

Computing details

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

	Fig. 1. View of the title compound (I), with displacement ellipsoids drawn at the 40% probability level.
	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-(2-Hydroxybenzylideneamino)-3-(1H-1,2,4-yriazol-1-ylmethyl)-1H-1,2,4- triazole-5(4H)-thione

Crystal data

C12H11N7OS	F(000) = 624
Mr = 301.34	Dx = 1.470 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4407 reflections
a = 8.3335 (9) Å	θ = 2.9–26.4°
b = 14.9777 (16) Å	µ = 0.25 mm^−1
c = 11.4724 (12) Å	T = 294 K
β = 107.990 (2)°	Block, yellow
V = 1361.9 (3) Å^3	0.24 × 0.22 × 0.20 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2794 independent reflections
Radiation source: fine-focus sealed tube	2360 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ϕ and ω scans	θmax = 26.4°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→7
Tmin = 0.941, Tmax = 0.951	k = −16→18
7581 measured reflections	l = −14→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0406P)^2 + 0.4772P] where P = (Fo^2 + 2Fc^2)/3
2794 reflections	(Δ/σ)max = 0.001
198 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.24099 (6)	0.05342 (3)	1.03693 (4)	0.04496 (14)
O1	−0.04626 (15)	0.37581 (7)	0.80700 (11)	0.0442 (3)
H1	0.013 (3)	0.3616 (14)	0.878 (2)	0.063 (6)*
N1	0.40905 (17)	0.53058 (9)	1.13906 (13)	0.0434 (3)
N2	0.22775 (15)	0.43147 (8)	1.15774 (11)	0.0314 (3)
N3	0.18802 (17)	0.44585 (9)	1.03499 (12)	0.0381 (3)
N4	0.30746 (17)	0.23425 (8)	1.29213 (11)	0.0360 (3)
N5	0.33087 (17)	0.15302 (9)	1.24430 (12)	0.0367 (3)
H5	0.406 (2)	0.1151 (13)	1.2895 (18)	0.054 (6)*
N6	0.14833 (15)	0.22013 (8)	1.10029 (10)	0.0295 (3)
N7	0.04316 (15)	0.25335 (8)	0.98900 (11)	0.0316 (3)
C1	0.2999 (2)	0.50609 (11)	1.02949 (15)	0.0418 (4)
H1A	0.3039	0.5302	0.9557	0.050*
C2	0.3588 (2)	0.48184 (11)	1.21707 (15)	0.0390 (4)
H2	0.4081	0.4826	1.3017	0.047*
C3	0.13501 (19)	0.36690 (10)	1.20714 (14)	0.0341 (3)
H3A	0.0162	0.3698	1.1606	0.041*
H3B	0.1465	0.3822	1.2915	0.041*
C4	0.19761 (18)	0.27407 (10)	1.20221 (12)	0.0302 (3)
C5	0.23881 (18)	0.14125 (9)	1.12697 (13)	0.0315 (3)
C6	−0.06507 (18)	0.19935 (10)	0.92130 (13)	0.0309 (3)
H6	−0.0729	0.1412	0.9475	0.037*
C7	−0.17580 (18)	0.22927 (10)	0.80306 (13)	0.0303 (3)
C8	−0.3023 (2)	0.17068 (11)	0.73623 (15)	0.0388 (4)
H8	−0.3132	0.1151	0.7692	0.047*
C9	−0.4106 (2)	0.19364 (12)	0.62293 (15)	0.0440 (4)
H9	−0.4949	0.1544	0.5806	0.053*
C10	−0.3927 (2)	0.27575 (12)	0.57264 (14)	0.0446 (4)
H10	−0.4645	0.2912	0.4957	0.054*
C11	−0.2693 (2)	0.33477 (11)	0.63586 (14)	0.0404 (4)
H11	−0.2583	0.3895	0.6008	0.048*
C12	−0.16075 (18)	0.31324 (10)	0.75192 (13)	0.0320 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0579 (3)	0.0314 (2)	0.0392 (2)	0.00696 (18)	0.00580 (19)	−0.00365 (16)
O1	0.0484 (7)	0.0350 (6)	0.0379 (6)	−0.0072 (5)	−0.0032 (5)	0.0051 (5)
N1	0.0392 (7)	0.0385 (7)	0.0485 (8)	−0.0093 (6)	0.0075 (6)	−0.0053 (6)
N2	0.0317 (6)	0.0282 (6)	0.0313 (6)	0.0002 (5)	0.0054 (5)	−0.0035 (5)
N3	0.0370 (7)	0.0384 (7)	0.0329 (7)	−0.0048 (6)	0.0019 (5)	0.0027 (5)
N4	0.0370 (7)	0.0367 (7)	0.0299 (6)	0.0008 (5)	0.0037 (5)	−0.0008 (5)
N5	0.0368 (7)	0.0353 (7)	0.0314 (7)	0.0059 (6)	0.0007 (6)	0.0029 (5)
N6	0.0310 (6)	0.0277 (6)	0.0257 (6)	0.0004 (5)	0.0027 (5)	0.0013 (5)
N7	0.0331 (6)	0.0296 (6)	0.0263 (6)	0.0016 (5)	0.0006 (5)	0.0031 (5)
C1	0.0413 (9)	0.0390 (9)	0.0413 (9)	−0.0050 (7)	0.0072 (7)	0.0052 (7)
C2	0.0376 (8)	0.0373 (8)	0.0368 (8)	−0.0027 (7)	0.0037 (7)	−0.0092 (7)
C3	0.0351 (8)	0.0345 (8)	0.0333 (7)	−0.0005 (6)	0.0117 (6)	−0.0031 (6)
C4	0.0299 (7)	0.0323 (7)	0.0266 (7)	−0.0033 (6)	0.0062 (6)	−0.0008 (5)
C5	0.0314 (7)	0.0297 (7)	0.0305 (7)	0.0015 (6)	0.0052 (6)	0.0041 (6)
C6	0.0306 (7)	0.0293 (7)	0.0318 (7)	0.0000 (6)	0.0082 (6)	0.0011 (6)
C7	0.0278 (7)	0.0331 (7)	0.0282 (7)	0.0023 (6)	0.0060 (6)	−0.0026 (6)
C8	0.0344 (8)	0.0384 (8)	0.0400 (8)	−0.0030 (6)	0.0065 (7)	−0.0051 (7)
C9	0.0331 (8)	0.0510 (10)	0.0400 (9)	−0.0027 (7)	−0.0003 (7)	−0.0128 (7)
C10	0.0387 (9)	0.0581 (11)	0.0277 (8)	0.0116 (8)	−0.0034 (7)	−0.0046 (7)
C11	0.0461 (9)	0.0390 (8)	0.0323 (8)	0.0080 (7)	0.0066 (7)	0.0042 (6)
C12	0.0299 (7)	0.0339 (8)	0.0297 (7)	0.0028 (6)	0.0054 (6)	−0.0033 (6)

Geometric parameters (Å, º)

S1—C5	1.6762 (15)	C1—H1A	0.9300
O1—C12	1.3474 (18)	C2—H2	0.9300
O1—H1	0.83 (2)	C3—C4	1.492 (2)
N1—C2	1.320 (2)	C3—H3A	0.9700
N1—C1	1.355 (2)	C3—H3B	0.9700
N2—C2	1.329 (2)	C6—C7	1.456 (2)
N2—N3	1.3606 (17)	C6—H6	0.9300
N2—C3	1.4575 (19)	C7—C8	1.403 (2)
N3—C1	1.313 (2)	C7—C12	1.410 (2)
N4—C4	1.2941 (19)	C8—C9	1.378 (2)
N4—N5	1.3730 (18)	C8—H8	0.9300
N5—C5	1.3392 (19)	C9—C10	1.386 (3)
N5—H5	0.89 (2)	C9—H9	0.9300
N6—C4	1.3755 (18)	C10—C11	1.380 (2)
N6—C5	1.3839 (18)	C10—H10	0.9300
N6—N7	1.3981 (16)	C11—C12	1.397 (2)
N7—C6	1.2799 (18)	C11—H11	0.9300
C12—O1—H1	113.4 (15)	N4—C4—C3	124.66 (13)
C2—N1—C1	102.49 (13)	N6—C4—C3	124.29 (12)
C2—N2—N3	109.82 (13)	N5—C5—N6	102.35 (12)
C2—N2—C3	128.91 (13)	N5—C5—S1	127.65 (11)
N3—N2—C3	121.25 (12)	N6—C5—S1	129.98 (11)
C1—N3—N2	102.07 (12)	N7—C6—C7	119.74 (13)
C4—N4—N5	104.04 (12)	N7—C6—H6	120.1
C5—N5—N4	114.22 (12)	C7—C6—H6	120.1
C5—N5—H5	125.9 (13)	C8—C7—C12	118.61 (13)
N4—N5—H5	119.8 (13)	C8—C7—C6	118.01 (13)
C4—N6—C5	108.31 (11)	C12—C7—C6	123.38 (13)
C4—N6—N7	120.37 (11)	C9—C8—C7	121.47 (15)
C5—N6—N7	130.61 (12)	C9—C8—H8	119.3
C6—N7—N6	117.05 (12)	C7—C8—H8	119.3
N3—C1—N1	115.14 (15)	C8—C9—C10	119.41 (15)
N3—C1—H1A	122.4	C8—C9—H9	120.3
N1—C1—H1A	122.4	C10—C9—H9	120.3
N1—C2—N2	110.46 (14)	C11—C10—C9	120.53 (15)
N1—C2—H2	124.8	C11—C10—H10	119.7
N2—C2—H2	124.8	C9—C10—H10	119.7
N2—C3—C4	111.71 (12)	C10—C11—C12	120.75 (15)
N2—C3—H3A	109.3	C10—C11—H11	119.6
C4—C3—H3A	109.3	C12—C11—H11	119.6
N2—C3—H3B	109.3	O1—C12—C11	116.29 (14)
C4—C3—H3B	109.3	O1—C12—C7	124.50 (13)
H3A—C3—H3B	107.9	C11—C12—C7	119.21 (14)
N4—C4—N6	111.03 (13)
C2—N2—N3—C1	−0.66 (16)	N4—N5—C5—N6	−1.39 (17)
C3—N2—N3—C1	−179.13 (13)	N4—N5—C5—S1	176.86 (11)
C4—N4—N5—C5	0.11 (18)	C4—N6—C5—N5	2.08 (15)
C4—N6—N7—C6	−144.62 (14)	N7—N6—C5—N5	172.20 (14)
C5—N6—N7—C6	46.3 (2)	C4—N6—C5—S1	−176.11 (12)
N2—N3—C1—N1	0.68 (19)	N7—N6—C5—S1	−6.0 (2)
C2—N1—C1—N3	−0.4 (2)	N6—N7—C6—C7	−178.65 (12)
C1—N1—C2—N2	−0.02 (18)	N7—C6—C7—C8	−174.66 (14)
N3—N2—C2—N1	0.44 (18)	N7—C6—C7—C12	6.3 (2)
C3—N2—C2—N1	178.76 (13)	C12—C7—C8—C9	0.0 (2)
C2—N2—C3—C4	−95.93 (17)	C6—C7—C8—C9	−179.13 (14)
N3—N2—C3—C4	82.22 (16)	C7—C8—C9—C10	1.1 (2)
N5—N4—C4—N6	1.29 (16)	C8—C9—C10—C11	−0.9 (3)
N5—N4—C4—C3	−177.52 (13)	C9—C10—C11—C12	−0.4 (3)
C5—N6—C4—N4	−2.22 (17)	C10—C11—C12—O1	−178.99 (15)
N7—N6—C4—N4	−173.54 (13)	C10—C11—C12—C7	1.5 (2)
C5—N6—C4—C3	176.59 (13)	C8—C7—C12—O1	179.25 (14)
N7—N6—C4—C3	5.3 (2)	C6—C7—C12—O1	−1.7 (2)
N2—C3—C4—N4	95.70 (17)	C8—C7—C12—C11	−1.3 (2)
N2—C3—C4—N6	−82.95 (17)	C6—C7—C12—C11	177.78 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···N1^i	0.89 (2)	1.97 (2)	2.8389 (19)	168.2 (18)
O1—H1···N3	0.83 (2)	2.32 (2)	2.9324 (17)	131.1 (19)
O1—H1···N7	0.83 (2)	2.03 (2)	2.7051 (17)	137 (2)
C3—H3B···S1^ii	0.97	2.85	3.8020 (16)	168
C6—H6···S1	0.93	2.82	3.3094 (15)	114

Symmetry codes: (i) −x+1, y−1/2, −z+5/2; (ii) x, −y+1/2, z+1/2.