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The title compound, C14H11N5S, was prepared by the reaction of 4-amino-5-(3-pyrid­yl)-1H-1,2,4-triazole-5(4H)-thione and benzaldehyde with ethanol at room temperature. The dihedral angles formed by the benzene and pyridine rings with the triazole ring are 46.2 (1) and 35.1 (2)°. There are weak inter- and intra­molecular hydrogen bonds in the crystal structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025573/wn2136sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025573/wn2136Isup2.hkl
Contains datablock I

CCDC reference: 654846

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.047
  • wR factor = 0.129
  • Data-to-parameter ratio = 16.2

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 40 Perc. PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1 C14 H11 N5 S
Alert level G REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values From the CIF: _diffrn_reflns_theta_max 26.97 From the CIF: _reflns_number_total 2928 From the CIF: _diffrn_reflns_limit_ max hkl 11. 0. 12. From the CIF: _diffrn_reflns_limit_ min hkl 0. -16. -16. TEST1: Expected hkl limits for theta max Calculated maximum hkl 11. 18. 16. Calculated minimum hkl -11. -18. -16.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 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

Comment top

Schiff bases have been used extensively as ligands in the field of coordination chemistry (Jian et al., 2006). They have biochemical and pharmacological applications. The recent growing interest in them is also due to their ability to form intramolecular hydrogen bonds by electron coupling between acid-base centers (Rozwadowski et al.,1999). The title compound has been synthesized and we report here its crystal structure.

In the crystal structure (Fig. 1), the dihedral angles formed by the phenyl and pyridine rings with the plane through the triazole ring and S atom are 46.2 (1) and 35.1 (2)°, respectively. The CS bond length (1.666 (3) Å) and C7N2 bond length (1.275 (3) Å) are in agreement with those observed earlier (Qin et al., 2006; Jian et al., 2006). Intramolecular C—H···S and C—H···N as well as intermolecular N—H···N hydrogen bonds are present in the crystal structure.

Related literature top

For related literature, see: Dallavalle et al. (2002); Jian et al. (2006); Qin et al. (2006); Rozwadowski et al. (1999).

Experimental top

A mixture of 4-amino-5-(3-pyridyl)-1H-1,2,4-triazole-5(4H)-thione (Dallavalle et al., 2002) (0.02 mol) and benzaldehyde (0.02 mol) was stirred with ethanol (50 mL) at 293 K for 5 h, affording the title compound (4.8 g, yield 86%). Single crystals suitable for X-ray measurements were obtained by recrystallization from acetone and ethanol (1:1) at room temperature.

Refinement top

H atoms were positioned geometrically and allowed to ride on their parent atoms, with N—H and C—H distances of 0.86 and 0.93 Å, respectively, and with Uiso(H) = 1.2Ueq of the parent atoms.

Structure description top

Schiff bases have been used extensively as ligands in the field of coordination chemistry (Jian et al., 2006). They have biochemical and pharmacological applications. The recent growing interest in them is also due to their ability to form intramolecular hydrogen bonds by electron coupling between acid-base centers (Rozwadowski et al.,1999). The title compound has been synthesized and we report here its crystal structure.

In the crystal structure (Fig. 1), the dihedral angles formed by the phenyl and pyridine rings with the plane through the triazole ring and S atom are 46.2 (1) and 35.1 (2)°, respectively. The CS bond length (1.666 (3) Å) and C7N2 bond length (1.275 (3) Å) are in agreement with those observed earlier (Qin et al., 2006; Jian et al., 2006). Intramolecular C—H···S and C—H···N as well as intermolecular N—H···N hydrogen bonds are present in the crystal structure.

For related literature, see: Dallavalle et al. (2002); Jian et al. (2006); Qin et al. (2006); Rozwadowski et al. (1999).

Computing details top

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL/PC (Sheldrick, 1997b); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level.
4-(Benzylideneamino)-3-(2-pyridyl)-1H-1,2,4-triazole-5(4H)-thione top
Crystal data top
C14H11N5SF(000) = 584
Mr = 281.34Dx = 1.365 Mg m3
Monoclinic, P21/cMelting point: 221.3 K
Hall symbol: -P 2y bcMo Kα radiation, λ = 0.71073 Å
a = 9.2400 (18) ÅCell parameters from 25 reflections
b = 14.217 (3) Åθ = 4–14°
c = 13.302 (4) ŵ = 0.23 mm1
β = 128.408 (19)°T = 295 K
V = 1369.3 (7) Å3Block, yellow
Z = 40.20 × 0.15 × 0.11 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.059
Radiation source: fine-focus sealed tubeθmax = 27.0°, θmin = 2.4°
Graphite monochromatorh = 011
ω scansk = 160
3100 measured reflectionsl = 1612
2928 independent reflections3 standard reflections every 100 reflections
1176 reflections with I > 2σ(I) intensity decay: none
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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129H-atom parameters constrained
S = 0.96 w = 1/[σ2(Fo2) + (0.0471P)2]
where P = (Fo2 + 2Fc2)/3
2928 reflections(Δ/σ)max < 0.001
181 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C14H11N5SV = 1369.3 (7) Å3
Mr = 281.34Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.2400 (18) ŵ = 0.23 mm1
b = 14.217 (3) ÅT = 295 K
c = 13.302 (4) Å0.20 × 0.15 × 0.11 mm
β = 128.408 (19)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.059
3100 measured reflections3 standard reflections every 100 reflections
2928 independent reflections intensity decay: none
1176 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.129H-atom parameters constrained
S = 0.96Δρmax = 0.23 e Å3
2928 reflectionsΔρmin = 0.20 e Å3
181 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
S10.15884 (15)0.05229 (6)0.09184 (9)0.0697 (3)
N10.3609 (3)0.11339 (15)0.0133 (2)0.0439 (6)
N20.2915 (3)0.15678 (16)0.1301 (2)0.0466 (7)
N30.4956 (4)0.11668 (17)0.1939 (2)0.0518 (7)
N40.3887 (4)0.03778 (17)0.1356 (2)0.0550 (7)
H4A0.37770.00450.17670.066*
N50.6386 (4)0.40531 (18)0.2188 (2)0.0566 (7)
C10.1107 (4)0.2359 (2)0.3790 (3)0.0573 (9)
H1A0.11920.27480.31940.069*
C20.0398 (5)0.2701 (3)0.4985 (3)0.0653 (10)
H2B0.00100.33230.51930.078*
C30.0262 (5)0.2125 (3)0.5872 (3)0.0717 (11)
H3B0.02160.23630.66760.086*
C40.0823 (5)0.1208 (3)0.5585 (4)0.0730 (11)
H4B0.07240.08220.61890.088*
C50.1541 (5)0.0858 (2)0.4383 (3)0.0594 (10)
H5B0.19210.02340.41840.071*
C60.1697 (4)0.1427 (2)0.3478 (3)0.0458 (8)
C70.2484 (4)0.1028 (2)0.2216 (3)0.0477 (8)
H7A0.26680.03830.20830.057*
C80.3023 (4)0.03192 (19)0.0087 (3)0.0473 (8)
C90.4751 (4)0.16280 (19)0.1012 (3)0.0439 (8)
C100.5540 (4)0.2550 (2)0.1144 (3)0.0406 (7)
C110.6108 (4)0.2834 (2)0.0441 (3)0.0569 (9)
H11A0.60210.24270.01410.068*
C120.6804 (5)0.3732 (2)0.0621 (3)0.0675 (10)
H12A0.72010.39380.01640.081*
C130.5736 (4)0.3186 (2)0.2011 (3)0.0477 (8)
H13A0.53880.29920.25020.057*
C140.6901 (5)0.4319 (2)0.1488 (3)0.0679 (11)
H14A0.73450.49270.15900.081*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0892 (7)0.0522 (5)0.0663 (6)0.0178 (5)0.0476 (6)0.0108 (5)
N10.0574 (18)0.0360 (14)0.0380 (15)0.0011 (13)0.0295 (14)0.0017 (12)
N20.0561 (19)0.0466 (15)0.0359 (15)0.0005 (13)0.0279 (14)0.0018 (13)
N30.0638 (19)0.0446 (16)0.0429 (15)0.0009 (14)0.0312 (15)0.0012 (13)
N40.076 (2)0.0422 (16)0.0499 (17)0.0016 (15)0.0403 (16)0.0089 (13)
N50.063 (2)0.0481 (17)0.0554 (18)0.0104 (14)0.0349 (17)0.0141 (14)
C10.060 (2)0.063 (2)0.049 (2)0.0082 (19)0.034 (2)0.0011 (18)
C20.066 (3)0.073 (3)0.053 (2)0.011 (2)0.036 (2)0.017 (2)
C30.050 (2)0.122 (4)0.037 (2)0.004 (2)0.024 (2)0.005 (2)
C40.075 (3)0.098 (3)0.051 (2)0.008 (3)0.041 (2)0.017 (2)
C50.063 (2)0.067 (2)0.047 (2)0.0085 (19)0.033 (2)0.0136 (18)
C60.042 (2)0.054 (2)0.039 (2)0.0049 (16)0.0238 (17)0.0068 (16)
C70.055 (2)0.0437 (18)0.047 (2)0.0003 (16)0.0332 (18)0.0029 (16)
C80.060 (2)0.0387 (18)0.0483 (19)0.0066 (16)0.0361 (18)0.0047 (15)
C90.053 (2)0.0405 (18)0.0396 (18)0.0048 (16)0.0298 (18)0.0003 (15)
C100.0418 (19)0.0408 (17)0.0349 (17)0.0020 (15)0.0216 (16)0.0026 (14)
C110.073 (3)0.054 (2)0.055 (2)0.0044 (18)0.045 (2)0.0101 (17)
C120.089 (3)0.063 (2)0.071 (3)0.016 (2)0.060 (2)0.007 (2)
C130.051 (2)0.051 (2)0.0405 (18)0.0034 (17)0.0280 (17)0.0004 (16)
C140.078 (3)0.049 (2)0.074 (3)0.0158 (19)0.046 (2)0.0077 (19)
Geometric parameters (Å, º) top
S1—C81.666 (3)C3—H3B0.9300
N1—C81.385 (3)C4—C51.388 (4)
N1—C91.389 (3)C4—H4B0.9300
N1—N21.403 (3)C5—C61.382 (4)
N2—C71.275 (3)C5—H5B0.9300
N3—C91.302 (3)C6—C71.467 (4)
N3—N41.372 (3)C7—H7A0.9300
N4—C81.349 (3)C9—C101.457 (4)
N4—H4A0.8600C10—C131.386 (4)
N5—C131.327 (4)C10—C111.387 (4)
N5—C141.336 (4)C11—C121.382 (4)
C1—C21.378 (4)C11—H11A0.9300
C1—C61.394 (4)C12—C141.381 (4)
C1—H1A0.9300C12—H12A0.9300
C2—C31.376 (4)C13—H13A0.9300
C2—H2B0.9300C14—H14A0.9300
C3—C41.367 (5)
C8—N1—C9108.7 (2)C1—C6—C7122.2 (3)
C8—N1—N2129.2 (2)N2—C7—C6119.9 (3)
C9—N1—N2120.4 (2)N2—C7—H7A120.1
C7—N2—N1116.7 (2)C6—C7—H7A120.1
C9—N3—N4104.3 (2)N4—C8—N1102.0 (2)
C8—N4—N3114.6 (2)N4—C8—S1127.3 (2)
C8—N4—H4A122.7N1—C8—S1130.7 (2)
N3—N4—H4A122.7N3—C9—N1110.4 (3)
C13—N5—C14117.2 (3)N3—C9—C10124.9 (3)
C2—C1—C6119.8 (3)N1—C9—C10124.7 (3)
C2—C1—H1A120.1C13—C10—C11117.6 (3)
C6—C1—H1A120.1C13—C10—C9118.9 (3)
C3—C2—C1120.3 (3)C11—C10—C9123.5 (3)
C3—C2—H2B119.9C12—C11—C10118.9 (3)
C1—C2—H2B119.9C12—C11—H11A120.6
C4—C3—C2120.7 (3)C10—C11—H11A120.6
C4—C3—H3B119.7C14—C12—C11118.9 (3)
C2—C3—H3B119.7C14—C12—H12A120.5
C3—C4—C5119.4 (3)C11—C12—H12A120.5
C3—C4—H4B120.3N5—C13—C10124.3 (3)
C5—C4—H4B120.3N5—C13—H13A117.8
C6—C5—C4120.7 (3)C10—C13—H13A117.8
C6—C5—H5B119.6N5—C14—C12123.0 (3)
C4—C5—H5B119.6N5—C14—H14A118.5
C5—C6—C1119.1 (3)C12—C14—H14A118.5
C5—C6—C7118.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···N5i0.861.962.823 (4)175
C7—H7A···S10.932.643.209 (4)120
C11—H11A···N20.932.572.970 (4)106
Symmetry code: (i) x+1, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC14H11N5S
Mr281.34
Crystal system, space groupMonoclinic, P21/c
Temperature (K)295
a, b, c (Å)9.2400 (18), 14.217 (3), 13.302 (4)
β (°) 128.408 (19)
V3)1369.3 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.23
Crystal size (mm)0.20 × 0.15 × 0.11
Data collection
DiffractometerEnraf-Nonius CAD-4
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3100, 2928, 1176
Rint0.059
(sin θ/λ)max1)0.638
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.129, 0.96
No. of reflections2928
No. of parameters181
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.23, 0.20

Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL/PC (Sheldrick, 1997b), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···N5i0.861.962.823 (4)175
C7—H7A···S10.932.643.209 (4)120
C11—H11A···N20.932.572.970 (4)106
Symmetry code: (i) x+1, y+1/2, z+1/2.
 

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