4-[(E)-2-Furylmethyl­eneamino]-3-phenyl-1H-1,2,4-triazole-5(4H)-thione

In the title mol­ecule, C₁₃H₁₀N₄OS, the triazole ring makes dihedral angles of 16.14 (9) and 58.51 (11)°, respectively, with the phenyl and furan rings. Intra­molecular C—H...N hydrogen bonds generate S(5) and S(6) ring motifs. In the crystal structure, centrosymmetrically related mol­ecules are linked via N—H...S hydrogen bonds to form dimeric pairs, which are inter­linked via C—H...O and C—H...π inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.044
• wR factor = 0.126
• Data-to-parameter ratio = 20.6

checkCIF/PLATON results

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Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     --  C1      ..       6.06 su
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Labels ..........          1

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 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
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check


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PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

Author Response: The authors FHK, SRJ were involved in the data collection, structure solution and preparation of publication material. The authors KVS, PSP, BK and SMD were involved in the synthesis of the compound in different phases.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

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S1. Comment

1,2,4-Triazoles and their derivatives are found to be associated with various biological activities such as anticonvulsant (Kane et al., 1990; Kkgzel et al., 2004), antifungal (Rollas et al., 1993), anticancer (Holla et al., 2003), anti-inflammatory (Modzelewska & Kalabun, 1999) and antibacterial properties (Glerman et al., 1997). Several compounds containing 1,2,4-triazole rings are well known as drugs. For example, fluconazole is used as an antimicrobial drug (Shujuan et al., 2004), while vorozole, letrozole and anastrozole are non-steroidal drugs used for the threatment of cancer (Clemons et al., 2004) and loreclezole is used as an anticonvulsant (Johnston, 2002) drug. In view of the above properties, we have synthesized the title compound and report here its crystal structure.

Bond lengths and angles in the title molecule (Fig. 1) are found to have normal values (Allen et al., 1987). The furan ring is planar to within ±0.002 (2) Å and the triazole ring is also planar with a maximum deviation of 0.016 (2) Å for atom C1. The triazole and phenyl rings are twisted away from each other by an angle of 16.14 (9)°. The dihedral angle between the furan and triazole rings is 58.51 (11)°. Intramolecular C—H···N hydrogen bonds generate S(5) and S(6) ring motifs (Bernstein et al., 1995).

The crystal structure is stabilized by intermolecular C—H···O and N—H···S hydrogen bonds together with C—H···π interactions involving the phenyl ring. The centrosymmetrically related molecules are linked by N—H···S hydrogen bonds to form a dimeric pair (Fig. 2) which are interlinked via C—H···O hydrogen bonds.

Related literature

For the biological activities of triazole derivatives, see: Clemons et al. (2004); Glerman et al. (1997); Holla et al. (2003); Johnston (2002); Kane et al. (1990); Kkgzel et al. (2004); Modzelewska & Kalabun (1999); Rollas et al. (1993); Shujuan et al. (2004); For bond-length data, see: Allen et al. (1987). For graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995). Cg1 is the centroid of the C3–C8 ring.

S2. Experimental

The title Schiff base compound was obtained by refluxing a mixture of 4-amino-5-methyl-2,4-dihydro-3H-1,2,4-triazole-3-thione (0.01 mol), furfural (0.01 mol) in ethanol (30 ml) and 2 drops of concentrated H₂SO₄ for 3 h. The solid product obtained was collected by filtration, washed with ethanol and dried. Single crystals suitable for X-ray analysis were obtained from acetone-N,N-dimethylformamide (DMF) (1:2) solution by slow evaporation (yield 63%; m.p. 451–453 K). Analysis for C₁₃H₁₀N₄SO, found (calculated) in %: C 57.63 (57.77), H 3.62 (3.7), N 20.6 (20.74), S 11.79 (11.85).

S3. Refinement

The N-bound H atom was located in a difference map and refined with a N-H distance restraint of 0.85 (1) Å. C-bound H atoms were positioned geometrically [C-H = 0.93%A] and refined using a riding model, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The crystal packing of the title compound, viewed along the b axis. Hydrogen bonds are shown as dashed lines.

4-[(E)-2-Furylmethyleneamino]-3-phenyl-1H-1,2,4- triazole-5(4H)-thione

Crystal data

C13H10N4OS	F(000) = 1120
Mr = 270.31	Dx = 1.464 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 5448 reflections
a = 27.4006 (6) Å	θ = 2.9–27.9°
b = 11.4940 (3) Å	µ = 0.26 mm^−1
c = 7.7886 (2) Å	T = 100 K
V = 2452.96 (10) Å^3	Block, orange
Z = 8	0.40 × 0.13 × 0.10 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	3627 independent reflections
Radiation source: fine-focus sealed tube	2573 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.072
ϕ and ω scans	θmax = 30.2°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −38→38
Tmin = 0.829, Tmax = 0.974	k = −16→16
40042 measured reflections	l = −10→10

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0649P)^2 + 0.3858P] where P = (Fo^2 + 2Fc^2)/3
3627 reflections	(Δ/σ)max = 0.001
176 parameters	Δρmax = 0.26 e Å^−3
1 restraint	Δρmin = −0.32 e Å^−3

Special details

Experimental. The data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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	0.494570 (15)	0.69781 (4)	0.50297 (6)	0.02259 (13)
O1	0.36669 (4)	1.02453 (10)	0.58350 (18)	0.0258 (3)
N1	0.44316 (5)	0.52097 (12)	0.6503 (2)	0.0225 (3)
N2	0.39895 (5)	0.49428 (12)	0.7222 (2)	0.0228 (3)
N3	0.40473 (5)	0.68093 (11)	0.66047 (19)	0.0190 (3)
N4	0.38912 (5)	0.79579 (12)	0.6319 (2)	0.0206 (3)
C1	0.44803 (6)	0.63262 (15)	0.6058 (2)	0.0203 (3)
C2	0.37554 (6)	0.59359 (14)	0.7269 (2)	0.0204 (4)
C3	0.32509 (6)	0.60514 (14)	0.7901 (2)	0.0198 (3)
C4	0.30539 (6)	0.51246 (15)	0.8824 (2)	0.0244 (4)
H4A	0.3247	0.4484	0.9086	0.029*
C5	0.25719 (6)	0.51543 (16)	0.9351 (3)	0.0267 (4)
H5A	0.2444	0.4533	0.9971	0.032*
C6	0.22781 (6)	0.60973 (16)	0.8967 (2)	0.0259 (4)
H6A	0.1954	0.6111	0.9320	0.031*
C7	0.24716 (6)	0.70213 (16)	0.8051 (3)	0.0255 (4)
H7A	0.2275	0.7656	0.7783	0.031*
C8	0.29558 (6)	0.70074 (15)	0.7530 (2)	0.0229 (4)
H8A	0.3084	0.7637	0.6931	0.028*
C9	0.41795 (6)	0.87250 (15)	0.6957 (2)	0.0212 (4)
H9A	0.4458	0.8494	0.7548	0.025*
C10	0.40718 (6)	0.99364 (15)	0.6757 (2)	0.0214 (4)
C11	0.42966 (7)	1.08948 (16)	0.7401 (3)	0.0268 (4)
H11A	0.4578	1.0913	0.8067	0.032*
C12	0.40148 (7)	1.18664 (15)	0.6854 (3)	0.0282 (4)
H12A	0.4075	1.2646	0.7095	0.034*
C13	0.36459 (7)	1.14332 (15)	0.5921 (3)	0.0289 (4)
H13A	0.3406	1.1883	0.5399	0.035*
H1N1	0.4628 (6)	0.4674 (14)	0.619 (3)	0.034 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0170 (2)	0.0210 (2)	0.0298 (3)	0.00050 (15)	0.00408 (17)	0.00147 (18)
O1	0.0210 (6)	0.0219 (6)	0.0344 (8)	0.0019 (5)	−0.0013 (5)	0.0001 (6)
N1	0.0169 (7)	0.0191 (7)	0.0316 (9)	0.0034 (5)	0.0022 (6)	0.0014 (6)
N2	0.0161 (7)	0.0206 (7)	0.0317 (9)	0.0010 (5)	0.0025 (6)	0.0013 (6)
N3	0.0153 (6)	0.0172 (7)	0.0244 (8)	0.0004 (5)	−0.0002 (6)	0.0008 (6)
N4	0.0185 (6)	0.0173 (7)	0.0260 (8)	0.0016 (5)	0.0010 (6)	0.0015 (6)
C1	0.0170 (7)	0.0208 (8)	0.0232 (9)	0.0014 (6)	−0.0020 (6)	−0.0018 (7)
C2	0.0182 (8)	0.0182 (8)	0.0247 (9)	−0.0013 (6)	−0.0014 (7)	0.0010 (7)
C3	0.0167 (7)	0.0215 (8)	0.0212 (8)	−0.0018 (6)	−0.0011 (6)	−0.0011 (7)
C4	0.0214 (8)	0.0256 (9)	0.0262 (9)	0.0001 (7)	0.0001 (7)	0.0040 (7)
C5	0.0240 (8)	0.0306 (10)	0.0255 (9)	−0.0038 (7)	0.0025 (7)	0.0058 (8)
C6	0.0199 (8)	0.0320 (10)	0.0259 (9)	−0.0012 (7)	0.0031 (7)	−0.0031 (8)
C7	0.0180 (8)	0.0231 (9)	0.0353 (10)	0.0026 (7)	0.0003 (7)	−0.0044 (8)
C8	0.0206 (8)	0.0204 (8)	0.0279 (10)	−0.0013 (6)	0.0008 (7)	0.0008 (7)
C9	0.0161 (7)	0.0240 (8)	0.0236 (9)	0.0006 (6)	0.0024 (7)	0.0003 (7)
C10	0.0169 (7)	0.0235 (9)	0.0238 (9)	−0.0008 (6)	0.0028 (7)	−0.0001 (7)
C11	0.0214 (8)	0.0254 (9)	0.0334 (10)	−0.0042 (7)	0.0033 (7)	−0.0027 (8)
C12	0.0280 (9)	0.0199 (9)	0.0366 (11)	−0.0031 (7)	0.0106 (8)	−0.0019 (8)
C13	0.0280 (9)	0.0216 (9)	0.0372 (11)	0.0054 (7)	0.0072 (8)	0.0050 (8)

Geometric parameters (Å, º)

S1—C1	1.6820 (17)	C5—C6	1.383 (3)
O1—C13	1.368 (2)	C5—H5A	0.93
O1—C10	1.368 (2)	C6—C7	1.385 (3)
N1—C1	1.336 (2)	C6—H6A	0.93
N1—N2	1.369 (2)	C7—C8	1.388 (2)
N1—H1N1	0.853 (9)	C7—H7A	0.93
N2—C2	1.310 (2)	C8—H8A	0.93
N3—C1	1.377 (2)	C9—C10	1.432 (2)
N3—C2	1.384 (2)	C9—H9A	0.93
N3—N4	1.4054 (18)	C10—C11	1.358 (2)
N4—C9	1.284 (2)	C11—C12	1.423 (3)
C2—C3	1.474 (2)	C11—H11A	0.93
C3—C4	1.394 (2)	C12—C13	1.341 (3)
C3—C8	1.395 (2)	C12—H12A	0.93
C4—C5	1.384 (2)	C13—H13A	0.93
C4—H4A	0.93
C13—O1—C10	105.50 (14)	C5—C6—C7	119.33 (16)
C1—N1—N2	114.19 (14)	C5—C6—H6A	120.3
C1—N1—H1N1	123.8 (15)	C7—C6—H6A	120.3
N2—N1—H1N1	120.9 (15)	C6—C7—C8	120.52 (17)
C2—N2—N1	104.44 (13)	C6—C7—H7A	119.7
C1—N3—C2	108.72 (13)	C8—C7—H7A	119.7
C1—N3—N4	126.29 (13)	C7—C8—C3	120.18 (16)
C2—N3—N4	124.37 (13)	C7—C8—H8A	119.9
C9—N4—N3	113.36 (14)	C3—C8—H8A	119.9
N1—C1—N3	102.77 (14)	N4—C9—C10	119.92 (16)
N1—C1—S1	128.84 (13)	N4—C9—H9A	120.0
N3—C1—S1	128.36 (13)	C10—C9—H9A	120.0
N2—C2—N3	109.79 (14)	C11—C10—O1	110.56 (15)
N2—C2—C3	123.18 (15)	C11—C10—C9	130.92 (17)
N3—C2—C3	127.01 (15)	O1—C10—C9	118.46 (15)
C4—C3—C8	119.00 (15)	C10—C11—C12	106.24 (17)
C4—C3—C2	117.83 (15)	C10—C11—H11A	126.9
C8—C3—C2	123.05 (15)	C12—C11—H11A	126.9
C5—C4—C3	120.26 (16)	C13—C12—C11	106.25 (16)
C5—C4—H4A	119.9	C13—C12—H12A	126.9
C3—C4—H4A	119.9	C11—C12—H12A	126.9
C6—C5—C4	120.71 (17)	C12—C13—O1	111.45 (16)
C6—C5—H5A	119.6	C12—C13—H13A	124.3
C4—C5—H5A	119.6	O1—C13—H13A	124.3
C1—N1—N2—C2	−1.5 (2)	C8—C3—C4—C5	0.4 (3)
C1—N3—N4—C9	−60.1 (2)	C2—C3—C4—C5	−175.78 (17)
C2—N3—N4—C9	129.83 (18)	C3—C4—C5—C6	0.3 (3)
N2—N1—C1—N3	2.8 (2)	C4—C5—C6—C7	−0.3 (3)
N2—N1—C1—S1	−175.45 (13)	C5—C6—C7—C8	−0.3 (3)
C2—N3—C1—N1	−2.91 (19)	C6—C7—C8—C3	1.0 (3)
N4—N3—C1—N1	−174.24 (15)	C4—C3—C8—C7	−1.0 (3)
C2—N3—C1—S1	175.32 (14)	C2—C3—C8—C7	174.91 (17)
N4—N3—C1—S1	4.0 (3)	N3—N4—C9—C10	179.42 (14)
N1—N2—C2—N3	−0.50 (19)	C13—O1—C10—C11	0.1 (2)
N1—N2—C2—C3	177.88 (17)	C13—O1—C10—C9	177.54 (16)
C1—N3—C2—N2	2.2 (2)	N4—C9—C10—C11	174.88 (19)
N4—N3—C2—N2	173.76 (15)	N4—C9—C10—O1	−2.0 (3)
C1—N3—C2—C3	−176.07 (17)	O1—C10—C11—C12	0.1 (2)
N4—N3—C2—C3	−4.5 (3)	C9—C10—C11—C12	−176.88 (18)
N2—C2—C3—C4	14.2 (3)	C10—C11—C12—C13	−0.3 (2)
N3—C2—C3—C4	−167.70 (17)	C11—C12—C13—O1	0.4 (2)
N2—C2—C3—C8	−161.76 (17)	C10—O1—C13—C12	−0.3 (2)
N3—C2—C3—C8	16.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···S1^i	0.85 (2)	2.42 (2)	3.265 (2)	169 (2)
C4—H4A···N2	0.93	2.55	2.859 (2)	100
C6—H6A···O1^ii	0.93	2.59	3.347 (2)	139
C8—H8A···N4	0.93	2.29	2.942 (2)	126
C5—H5A···Cg1^iii	0.93	2.92	3.522 (2)	123

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