Crystal structure of (E)-3-(4-hy­droxy­benz­yl)-4-{[4-(methyl­sulfan­yl)benzyl­idene]amino}-1H-1,2,4-triazole-5(4H)-thione

Abstract

In the title compound, C₁₇H₁₆N₄OS₂, the triazole and methyl­thio­benzyl­idene rings are nearly coplanar, making a dihedral angle of 6.52 (12)°. An intra­molecular C—H⋯S hydrogen bond forms an S(6) ring motif. The hy­droxy­benzyl ring is almost normal to the triazole and methyl­thio­benzyl­idene rings, making dihedral angles of 78.56 (12) and 84.79 (11)°, respectively. In the crystal, mol­ecules are linked through O—H⋯N and N—H⋯O hydrogen bonds, forming layers parallel to the ac plane. The layers are linked via C—H⋯N hydrogen bonds, forming a three-dimensional structure. In addition, a short π–π inter­action is observed [inter-centroid distance = 3.764 (3) Å], involving inversion-related methyl­thio­benzyl­idene rings.

Related literature  

For the structure of a related compound, see: Manjula et al. (2015 ▸).

Experimental  

Crystal data  

• C₁₇H₁₆N₄OS₂

• M _r = 356.46

• Monoclinic,

• a = 7.739 (5) Å

• b = 28.161 (16) Å

• c = 7.945 (4) Å

• β = 100.407 (11)°

• V = 1703.0 (17) ų

• Z = 4

• Mo Kα radiation

• μ = 0.32 mm⁻¹

• T = 293 K

• 0.57 × 0.34 × 0.24 mm

Data collection  

• Rigaku Saturn724+ diffractometer

• Absorption correction: numerical (NUMABS; Rigaku, 1999 ▸) T _min = 0.895, T _max = 0.954

• 8210 measured reflections

• 3017 independent reflections

• 2200 reflections with I > 2σ(I)

• R _int = 0.031

Refinement  

• R[F ² > 2σ(F ²)] = 0.047

• wR(F ²) = 0.107

• S = 1.06

• 3017 reflections

• 217 parameters

• H-atom parameters constrained

• Δρ_max = 0.16 e Å⁻³

• Δρ_min = −0.17 e Å⁻³

Data collection: CrystalClear (Rigaku, 2011 ▸); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009 ▸).

Supplementary Material

CCDC reference: 1437595

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯S1	0.93	2.52	3.267 (3)	138
O1—H1⋯N2i	0.82	2.03	2.806 (3)	159
N1—H1A⋯O1ii	0.86	1.98	2.816 (3)	164
C17—H17C⋯N4iii	0.96	2.62	3.472 (4)	148

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

S1. Comment

The title compound was synthesized, crystallized and its crystal structure is presented as part of our work on 3-methyl-1H-1,2,4-triazole-5(4H)-thione derivatives (Manjula et al., 2015).

The molecular structure of the title compound is as shown in Fig 1. The methylsulfanylbenzylidene and triazole rings are almost coplanar with a dihedral angle of 6.52 (12) °. The hydroxybenzyl ring makes dihedral angles of 78.56 (12) ° and 84.79 (11) ° with the triazole and methylthiobenzylidene rings, respectively. An intramolecular interaction of the type C10—H10···S1 is observed (Fig. 1 and Table 1).

In the crystal, the molecules are connected through O1—H1···N2 and N1—H1A···O1 hydrogen bonds (Table 1) forming layers parallel to (010). The layers are linked by C17—H17C···N4 hydrogen bonds forming a three-dimensional structure (Fig. 2 and Table 1) . In addition, a parallel slipped π–π (Cg···Cgⁱ) interaction is observed with an inter-centroid distance of 3.764 (3) Å [Cg is the centroid of ring C11—C16; inter-planar distance = 3.500 (1) Å; slippage 1.384 Å; symmetry code: (i) -x, -y+1, -z+1].

S2. Experimental

The synthesis of title compound, (3), is illustrated in Fig. 3. A suspension of 4-(methylthio)benzaldehyde (2) (0.01 mol) in ethanol (15 ml) was added to 4-amino-3-(4-hydroxybenzyl)-1H-1,2,4-triazole-5(4H)-thione (1) (0.01 mol) and heated until a clear solution was obtained. To this a few drops of conc. H₂SO₄ were added as a catalyst and the mixture was refluxed for 36 h on a water bath. The precipitate formed was filtered and recrystallized from methanol to give the titled compound. Single crystals were obtained by recrystallization from acetic acid (m.p. 469—471 K).

S3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The H atoms were fixed geometrically (O-H = 0.82 Å, N-H = 0.86 Å, and C—H = 0.93–0.97 Å) and allowed to ride on their parent atoms with U_iso(H) = 1.2U_eq(O,N,C).

Figures

Fig. 1.

A view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level and the intramolecular C—H···S hydrogen bond is drawn as a dashed line (see Table 1).

Fig. 2.

A viewed along the c axis of the crystal packing of the title compound. Hydrogen bonds are drawn as a dashed lines (see Table 1), and H atoms not involved in hydrogen bonding have been omitted for clarity.

Fig. 3.

Reaction scheme.

Crystal data

C17H16N4OS2	F(000) = 744
Mr = 356.46	Dx = 1.390 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71075 Å
a = 7.739 (5) Å	Cell parameters from 2021 reflections
b = 28.161 (16) Å	θ = 3.0–25.3°
c = 7.945 (4) Å	µ = 0.32 mm−1
β = 100.407 (11)°	T = 293 K
V = 1703.0 (17) Å3	Prism, yellow
Z = 4	0.57 × 0.34 × 0.24 mm

Data collection

Rigaku Saturn724+ diffractometer	2200 reflections with I > 2σ(I)
Detector resolution: 7.111 pixels mm-1	Rint = 0.031
profile data from ω–scans	θmax = 25.3°, θmin = 3.0°
Absorption correction: numerical (NUMABS; Rigaku, 1999)	h = −9→9
Tmin = 0.895, Tmax = 0.954	k = −33→33
8210 measured reflections	l = −9→6
3017 independent reflections

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047	H-atom parameters constrained
wR(F2) = 0.107	w = 1/[σ2(Fo2) + (0.0424P)2 + 0.239P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
3017 reflections	Δρmax = 0.16 e Å−3
217 parameters	Δρmin = −0.17 e Å−3
0 restraints

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.53353 (10)	0.58782 (3)	1.04260 (8)	0.0612 (2)
S2	0.00577 (11)	0.40779 (3)	0.16264 (10)	0.0797 (3)
O1	−0.2083 (2)	0.71862 (6)	0.21145 (19)	0.0526 (5)
H1	−0.2399	0.7431	0.2531	0.063*
N1	0.6203 (2)	0.67074 (7)	0.9170 (2)	0.0482 (5)
H1A	0.6603	0.6818	1.0173	0.058*
N2	0.6227 (3)	0.69644 (7)	0.7707 (2)	0.0469 (5)
N3	0.5039 (2)	0.62570 (6)	0.7141 (2)	0.0386 (5)
N4	0.4256 (2)	0.59134 (7)	0.5984 (2)	0.0410 (5)
C1	0.5514 (3)	0.62736 (9)	0.8925 (3)	0.0414 (6)
C2	0.5495 (3)	0.66794 (8)	0.6491 (3)	0.0403 (6)
C3	0.5120 (3)	0.68017 (9)	0.4640 (3)	0.0490 (6)
H3A	0.5476	0.6539	0.3991	0.059*
H3B	0.5815	0.7077	0.4448	0.059*
C4	0.3195 (3)	0.69085 (8)	0.3991 (3)	0.0401 (6)
C5	0.2392 (3)	0.72987 (8)	0.4562 (3)	0.0482 (6)
H5	0.3045	0.7500	0.5360	0.058*
C6	0.0633 (3)	0.73960 (8)	0.3971 (3)	0.0465 (6)
H6	0.0115	0.7661	0.4371	0.056*
C7	−0.0348 (3)	0.70997 (8)	0.2788 (3)	0.0407 (6)
C8	0.0426 (3)	0.67050 (8)	0.2227 (3)	0.0494 (6)
H8	−0.0234	0.6499	0.1447	0.059*
C9	0.2177 (3)	0.66139 (8)	0.2818 (3)	0.0470 (6)
H9	0.2689	0.6348	0.2418	0.056*
C10	0.3768 (3)	0.55258 (9)	0.6531 (3)	0.0459 (6)
H10	0.3949	0.5468	0.7702	0.055*
C11	0.2918 (3)	0.51667 (8)	0.5332 (3)	0.0414 (6)
C12	0.2277 (3)	0.47597 (9)	0.5961 (3)	0.0497 (6)
H12	0.2421	0.4717	0.7138	0.060*
C13	0.1424 (3)	0.44141 (9)	0.4884 (4)	0.0539 (7)
H13	0.1007	0.4142	0.5337	0.065*
C14	0.1194 (3)	0.44748 (9)	0.3131 (3)	0.0497 (6)
C15	0.1865 (3)	0.48812 (9)	0.2491 (3)	0.0524 (7)
H15	0.1737	0.4923	0.1314	0.063*
C16	0.2715 (3)	0.52218 (9)	0.3575 (3)	0.0477 (6)
H16	0.3157	0.5491	0.3125	0.057*
C17	−0.0520 (4)	0.35993 (11)	0.2856 (4)	0.0858 (10)
H17A	−0.1153	0.3365	0.2109	0.103*
H17B	0.0526	0.3459	0.3497	0.103*
H17C	−0.1246	0.3714	0.3629	0.103*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0752 (5)	0.0629 (5)	0.0440 (4)	0.0047 (4)	0.0069 (3)	0.0112 (3)
S2	0.0756 (6)	0.0803 (6)	0.0843 (6)	−0.0262 (5)	0.0171 (4)	−0.0331 (5)
O1	0.0503 (11)	0.0521 (11)	0.0503 (10)	0.0091 (9)	−0.0044 (8)	−0.0126 (8)
N1	0.0483 (13)	0.0511 (13)	0.0395 (12)	−0.0014 (10)	−0.0079 (9)	−0.0028 (10)
N2	0.0412 (12)	0.0476 (12)	0.0472 (12)	−0.0023 (10)	−0.0044 (9)	0.0051 (10)
N3	0.0346 (11)	0.0411 (11)	0.0378 (11)	0.0003 (9)	0.0006 (9)	0.0015 (9)
N4	0.0386 (11)	0.0393 (12)	0.0436 (11)	−0.0004 (9)	0.0037 (9)	−0.0020 (9)
C1	0.0350 (13)	0.0458 (14)	0.0408 (14)	0.0068 (11)	0.0003 (11)	0.0002 (11)
C2	0.0316 (13)	0.0440 (14)	0.0429 (14)	0.0006 (11)	0.0003 (11)	0.0046 (11)
C3	0.0462 (15)	0.0543 (16)	0.0460 (15)	−0.0058 (13)	0.0069 (12)	0.0074 (12)
C4	0.0475 (14)	0.0401 (14)	0.0321 (13)	−0.0017 (11)	0.0050 (11)	0.0062 (10)
C5	0.0586 (17)	0.0409 (14)	0.0401 (14)	−0.0040 (13)	−0.0043 (12)	−0.0070 (11)
C6	0.0572 (17)	0.0395 (14)	0.0408 (14)	0.0062 (12)	0.0031 (12)	−0.0076 (11)
C7	0.0479 (15)	0.0406 (14)	0.0310 (12)	0.0054 (12)	−0.0003 (11)	0.0018 (10)
C8	0.0614 (17)	0.0404 (14)	0.0394 (14)	0.0050 (13)	−0.0095 (12)	−0.0086 (11)
C9	0.0564 (17)	0.0400 (14)	0.0418 (14)	0.0114 (12)	0.0014 (12)	−0.0044 (11)
C10	0.0437 (15)	0.0490 (16)	0.0435 (14)	0.0027 (12)	0.0036 (11)	0.0025 (12)
C11	0.0338 (13)	0.0399 (14)	0.0492 (15)	0.0039 (11)	0.0044 (11)	0.0015 (11)
C12	0.0501 (15)	0.0494 (16)	0.0467 (15)	0.0022 (13)	0.0013 (12)	0.0054 (12)
C13	0.0489 (16)	0.0422 (15)	0.0712 (19)	−0.0012 (13)	0.0121 (14)	0.0045 (13)
C14	0.0373 (14)	0.0497 (16)	0.0635 (18)	0.0009 (12)	0.0126 (12)	−0.0084 (13)
C15	0.0505 (16)	0.0605 (17)	0.0456 (15)	0.0015 (14)	0.0071 (12)	−0.0031 (13)
C16	0.0473 (15)	0.0461 (15)	0.0511 (16)	−0.0039 (12)	0.0125 (12)	0.0036 (12)
C17	0.063 (2)	0.0600 (19)	0.139 (3)	−0.0127 (16)	0.031 (2)	−0.029 (2)

Geometric parameters (Å, º)

S1—C1	1.655 (2)	C6—H6	0.9300
S2—C14	1.752 (3)	C6—C7	1.377 (3)
S2—C17	1.769 (3)	C7—C8	1.375 (3)
O1—H1	0.8200	C8—H8	0.9300
O1—C7	1.374 (3)	C8—C9	1.376 (3)
N1—H1A	0.8600	C9—H9	0.9300
N1—N2	1.372 (2)	C10—H10	0.9300
N1—C1	1.333 (3)	C10—C11	1.462 (3)
N2—C2	1.304 (3)	C11—C12	1.378 (3)
N3—N4	1.396 (2)	C11—C16	1.386 (3)
N3—C1	1.399 (3)	C12—H12	0.9300
N3—C2	1.368 (3)	C12—C13	1.382 (3)
N4—C10	1.258 (3)	C13—H13	0.9300
C2—C3	1.487 (3)	C13—C14	1.383 (3)
C3—H3A	0.9700	C14—C15	1.390 (3)
C3—H3B	0.9700	C15—H15	0.9300
C3—C4	1.517 (3)	C15—C16	1.375 (3)
C4—C5	1.379 (3)	C16—H16	0.9300
C4—C9	1.383 (3)	C17—H17A	0.9600
C5—H5	0.9300	C17—H17B	0.9600
C5—C6	1.385 (3)	C17—H17C	0.9600
C14—S2—C17	104.78 (14)	C7—C8—H8	120.0
C7—O1—H1	109.5	C7—C8—C9	120.0 (2)
N2—N1—H1A	122.4	C9—C8—H8	120.0
C1—N1—H1A	122.4	C4—C9—H9	119.2
C1—N1—N2	115.23 (18)	C8—C9—C4	121.6 (2)
C2—N2—N1	103.43 (19)	C8—C9—H9	119.2
N4—N3—C1	133.95 (19)	N4—C10—H10	119.9
C2—N3—N4	117.69 (18)	N4—C10—C11	120.2 (2)
C2—N3—C1	108.36 (19)	C11—C10—H10	119.9
C10—N4—N3	119.70 (19)	C12—C11—C10	119.3 (2)
N1—C1—S1	126.50 (18)	C12—C11—C16	118.4 (2)
N1—C1—N3	101.73 (19)	C16—C11—C10	122.3 (2)
N3—C1—S1	131.78 (19)	C11—C12—H12	119.2
N2—C2—N3	111.2 (2)	C11—C12—C13	121.6 (2)
N2—C2—C3	124.8 (2)	C13—C12—H12	119.2
N3—C2—C3	123.9 (2)	C12—C13—H13	120.1
C2—C3—H3A	109.0	C12—C13—C14	119.8 (2)
C2—C3—H3B	109.0	C14—C13—H13	120.1
C2—C3—C4	112.74 (18)	C13—C14—S2	124.5 (2)
H3A—C3—H3B	107.8	C13—C14—C15	118.8 (2)
C4—C3—H3A	109.0	C15—C14—S2	116.8 (2)
C4—C3—H3B	109.0	C14—C15—H15	119.5
C5—C4—C3	121.3 (2)	C16—C15—C14	120.9 (2)
C5—C4—C9	117.7 (2)	C16—C15—H15	119.5
C9—C4—C3	121.0 (2)	C11—C16—H16	119.8
C4—C5—H5	119.3	C15—C16—C11	120.5 (2)
C4—C5—C6	121.3 (2)	C15—C16—H16	119.8
C6—C5—H5	119.3	S2—C17—H17A	109.5
C5—C6—H6	120.1	S2—C17—H17B	109.5
C7—C6—C5	119.9 (2)	S2—C17—H17C	109.5
C7—C6—H6	120.1	H17A—C17—H17B	109.5
O1—C7—C6	122.5 (2)	H17A—C17—H17C	109.5
O1—C7—C8	118.0 (2)	H17B—C17—H17C	109.5
C8—C7—C6	119.5 (2)
S2—C14—C15—C16	177.44 (19)	C2—C3—C4—C5	65.8 (3)
O1—C7—C8—C9	177.6 (2)	C2—C3—C4—C9	−113.4 (2)
N1—N2—C2—N3	−0.7 (2)	C3—C4—C5—C6	−179.9 (2)
N1—N2—C2—C3	176.7 (2)	C3—C4—C9—C8	179.6 (2)
N2—N1—C1—S1	178.79 (16)	C4—C5—C6—C7	0.0 (3)
N2—N1—C1—N3	−0.8 (2)	C5—C4—C9—C8	0.3 (3)
N2—C2—C3—C4	−103.6 (3)	C5—C6—C7—O1	−177.9 (2)
N3—N4—C10—C11	178.90 (18)	C5—C6—C7—C8	1.0 (3)
N3—C2—C3—C4	73.4 (3)	C6—C7—C8—C9	−1.4 (3)
N4—N3—C1—S1	0.2 (4)	C7—C8—C9—C4	0.7 (4)
N4—N3—C1—N1	179.7 (2)	C9—C4—C5—C6	−0.7 (3)
N4—N3—C2—N2	−179.30 (18)	C10—C11—C12—C13	178.4 (2)
N4—N3—C2—C3	3.4 (3)	C10—C11—C16—C15	−178.2 (2)
N4—C10—C11—C12	−175.2 (2)	C11—C12—C13—C14	−0.3 (4)
N4—C10—C11—C16	4.2 (3)	C12—C11—C16—C15	1.1 (3)
C1—N1—N2—C2	0.9 (3)	C12—C13—C14—S2	−177.14 (19)
C1—N3—N4—C10	2.8 (3)	C12—C13—C14—C15	1.4 (4)
C1—N3—C2—N2	0.2 (3)	C13—C14—C15—C16	−1.2 (4)
C1—N3—C2—C3	−177.1 (2)	C14—C15—C16—C11	−0.1 (4)
C2—N3—N4—C10	−177.9 (2)	C16—C11—C12—C13	−1.0 (4)
C2—N3—C1—S1	−179.21 (18)	C17—S2—C14—C13	−3.9 (2)
C2—N3—C1—N1	0.3 (2)	C17—S2—C14—C15	177.60 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···S1	0.93	2.52	3.267 (3)	138
O1—H1···N2i	0.82	2.03	2.806 (3)	159
N1—H1A···O1ii	0.86	1.98	2.816 (3)	164
C17—H17C···N4iii	0.96	2.62	3.472 (4)	148

Symmetry codes: (i) x−1, −y+3/2, z−1/2; (ii) x+1, y, z+1; (iii) −x, −y+1, −z+1.