Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025573/wn2136sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025573/wn2136Isup2.hkl |
CCDC reference: 654846
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (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
For related literature, see: Dallavalle et al. (2002); Jian et al. (2006); Qin et al. (2006); Rozwadowski et al. (1999).
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.
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.
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 C═S bond length (1.666 (3) Å) and C7═N2 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).
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).
Fig. 1. The molecular structure of the title compound with the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. |
C14H11N5S | F(000) = 584 |
Mr = 281.34 | Dx = 1.365 Mg m−3 |
Monoclinic, P21/c | Melting point: 221.3 K |
Hall symbol: -P 2y bc | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2400 (18) Å | Cell parameters from 25 reflections |
b = 14.217 (3) Å | θ = 4–14° |
c = 13.302 (4) Å | µ = 0.23 mm−1 |
β = 128.408 (19)° | T = 295 K |
V = 1369.3 (7) Å3 | Block, yellow |
Z = 4 | 0.20 × 0.15 × 0.11 mm |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.059 |
Radiation source: fine-focus sealed tube | θmax = 27.0°, θmin = 2.4° |
Graphite monochromator | h = 0→11 |
ω scans | k = −16→0 |
3100 measured reflections | l = −16→12 |
2928 independent reflections | 3 standard reflections every 100 reflections |
1176 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H-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 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C14H11N5S | V = 1369.3 (7) Å3 |
Mr = 281.34 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.2400 (18) Å | µ = 0.23 mm−1 |
b = 14.217 (3) Å | T = 295 K |
c = 13.302 (4) Å | 0.20 × 0.15 × 0.11 mm |
β = 128.408 (19)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.059 |
3100 measured reflections | 3 standard reflections every 100 reflections |
2928 independent reflections | intensity decay: none |
1176 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.23 e Å−3 |
2928 reflections | Δρmin = −0.20 e Å−3 |
181 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 | 0.15884 (15) | 0.05229 (6) | −0.09184 (9) | 0.0697 (3) | |
N1 | 0.3609 (3) | −0.11339 (15) | −0.0133 (2) | 0.0439 (6) | |
N2 | 0.2915 (3) | −0.15678 (16) | −0.1301 (2) | 0.0466 (7) | |
N3 | 0.4956 (4) | −0.11668 (17) | 0.1939 (2) | 0.0518 (7) | |
N4 | 0.3887 (4) | −0.03778 (17) | 0.1356 (2) | 0.0550 (7) | |
H4A | 0.3777 | 0.0045 | 0.1767 | 0.066* | |
N5 | 0.6386 (4) | −0.40531 (18) | 0.2188 (2) | 0.0566 (7) | |
C1 | 0.1107 (4) | −0.2359 (2) | −0.3790 (3) | 0.0573 (9) | |
H1A | 0.1192 | −0.2748 | −0.3194 | 0.069* | |
C2 | 0.0398 (5) | −0.2701 (3) | −0.4985 (3) | 0.0653 (10) | |
H2B | 0.0010 | −0.3323 | −0.5193 | 0.078* | |
C3 | 0.0262 (5) | −0.2125 (3) | −0.5872 (3) | 0.0717 (11) | |
H3B | −0.0216 | −0.2363 | −0.6676 | 0.086* | |
C4 | 0.0823 (5) | −0.1208 (3) | −0.5585 (4) | 0.0730 (11) | |
H4B | 0.0724 | −0.0822 | −0.6189 | 0.088* | |
C5 | 0.1541 (5) | −0.0858 (2) | −0.4383 (3) | 0.0594 (10) | |
H5B | 0.1921 | −0.0234 | −0.4184 | 0.071* | |
C6 | 0.1697 (4) | −0.1427 (2) | −0.3478 (3) | 0.0458 (8) | |
C7 | 0.2484 (4) | −0.1028 (2) | −0.2216 (3) | 0.0477 (8) | |
H7A | 0.2668 | −0.0383 | −0.2083 | 0.057* | |
C8 | 0.3023 (4) | −0.03192 (19) | 0.0087 (3) | 0.0473 (8) | |
C9 | 0.4751 (4) | −0.16280 (19) | 0.1012 (3) | 0.0439 (8) | |
C10 | 0.5540 (4) | −0.2550 (2) | 0.1144 (3) | 0.0406 (7) | |
C11 | 0.6108 (4) | −0.2834 (2) | 0.0441 (3) | 0.0569 (9) | |
H11A | 0.6021 | −0.2427 | −0.0141 | 0.068* | |
C12 | 0.6804 (5) | −0.3732 (2) | 0.0621 (3) | 0.0675 (10) | |
H12A | 0.7201 | −0.3938 | 0.0164 | 0.081* | |
C13 | 0.5736 (4) | −0.3186 (2) | 0.2011 (3) | 0.0477 (8) | |
H13A | 0.5388 | −0.2992 | 0.2502 | 0.057* | |
C14 | 0.6901 (5) | −0.4319 (2) | 0.1488 (3) | 0.0679 (11) | |
H14A | 0.7345 | −0.4927 | 0.1590 | 0.081* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0892 (7) | 0.0522 (5) | 0.0663 (6) | 0.0178 (5) | 0.0476 (6) | 0.0108 (5) |
N1 | 0.0574 (18) | 0.0360 (14) | 0.0380 (15) | −0.0011 (13) | 0.0295 (14) | −0.0017 (12) |
N2 | 0.0561 (19) | 0.0466 (15) | 0.0359 (15) | −0.0005 (13) | 0.0279 (14) | −0.0018 (13) |
N3 | 0.0638 (19) | 0.0446 (16) | 0.0429 (15) | 0.0009 (14) | 0.0312 (15) | −0.0012 (13) |
N4 | 0.076 (2) | 0.0422 (16) | 0.0499 (17) | −0.0016 (15) | 0.0403 (16) | −0.0089 (13) |
N5 | 0.063 (2) | 0.0481 (17) | 0.0554 (18) | 0.0104 (14) | 0.0349 (17) | 0.0141 (14) |
C1 | 0.060 (2) | 0.063 (2) | 0.049 (2) | −0.0082 (19) | 0.034 (2) | −0.0011 (18) |
C2 | 0.066 (3) | 0.073 (3) | 0.053 (2) | −0.011 (2) | 0.036 (2) | −0.017 (2) |
C3 | 0.050 (2) | 0.122 (4) | 0.037 (2) | 0.004 (2) | 0.024 (2) | −0.005 (2) |
C4 | 0.075 (3) | 0.098 (3) | 0.051 (2) | 0.008 (3) | 0.041 (2) | 0.017 (2) |
C5 | 0.063 (2) | 0.067 (2) | 0.047 (2) | 0.0085 (19) | 0.033 (2) | 0.0136 (18) |
C6 | 0.042 (2) | 0.054 (2) | 0.039 (2) | 0.0049 (16) | 0.0238 (17) | 0.0068 (16) |
C7 | 0.055 (2) | 0.0437 (18) | 0.047 (2) | −0.0003 (16) | 0.0332 (18) | 0.0029 (16) |
C8 | 0.060 (2) | 0.0387 (18) | 0.0483 (19) | −0.0066 (16) | 0.0361 (18) | −0.0047 (15) |
C9 | 0.053 (2) | 0.0405 (18) | 0.0396 (18) | −0.0048 (16) | 0.0298 (18) | 0.0003 (15) |
C10 | 0.0418 (19) | 0.0408 (17) | 0.0349 (17) | −0.0020 (15) | 0.0216 (16) | 0.0026 (14) |
C11 | 0.073 (3) | 0.054 (2) | 0.055 (2) | 0.0044 (18) | 0.045 (2) | 0.0101 (17) |
C12 | 0.089 (3) | 0.063 (2) | 0.071 (3) | 0.016 (2) | 0.060 (2) | 0.007 (2) |
C13 | 0.051 (2) | 0.051 (2) | 0.0405 (18) | −0.0034 (17) | 0.0280 (17) | 0.0004 (16) |
C14 | 0.078 (3) | 0.049 (2) | 0.074 (3) | 0.0158 (19) | 0.046 (2) | 0.0077 (19) |
S1—C8 | 1.666 (3) | C3—H3B | 0.9300 |
N1—C8 | 1.385 (3) | C4—C5 | 1.388 (4) |
N1—C9 | 1.389 (3) | C4—H4B | 0.9300 |
N1—N2 | 1.403 (3) | C5—C6 | 1.382 (4) |
N2—C7 | 1.275 (3) | C5—H5B | 0.9300 |
N3—C9 | 1.302 (3) | C6—C7 | 1.467 (4) |
N3—N4 | 1.372 (3) | C7—H7A | 0.9300 |
N4—C8 | 1.349 (3) | C9—C10 | 1.457 (4) |
N4—H4A | 0.8600 | C10—C13 | 1.386 (4) |
N5—C13 | 1.327 (4) | C10—C11 | 1.387 (4) |
N5—C14 | 1.336 (4) | C11—C12 | 1.382 (4) |
C1—C2 | 1.378 (4) | C11—H11A | 0.9300 |
C1—C6 | 1.394 (4) | C12—C14 | 1.381 (4) |
C1—H1A | 0.9300 | C12—H12A | 0.9300 |
C2—C3 | 1.376 (4) | C13—H13A | 0.9300 |
C2—H2B | 0.9300 | C14—H14A | 0.9300 |
C3—C4 | 1.367 (5) | ||
C8—N1—C9 | 108.7 (2) | C1—C6—C7 | 122.2 (3) |
C8—N1—N2 | 129.2 (2) | N2—C7—C6 | 119.9 (3) |
C9—N1—N2 | 120.4 (2) | N2—C7—H7A | 120.1 |
C7—N2—N1 | 116.7 (2) | C6—C7—H7A | 120.1 |
C9—N3—N4 | 104.3 (2) | N4—C8—N1 | 102.0 (2) |
C8—N4—N3 | 114.6 (2) | N4—C8—S1 | 127.3 (2) |
C8—N4—H4A | 122.7 | N1—C8—S1 | 130.7 (2) |
N3—N4—H4A | 122.7 | N3—C9—N1 | 110.4 (3) |
C13—N5—C14 | 117.2 (3) | N3—C9—C10 | 124.9 (3) |
C2—C1—C6 | 119.8 (3) | N1—C9—C10 | 124.7 (3) |
C2—C1—H1A | 120.1 | C13—C10—C11 | 117.6 (3) |
C6—C1—H1A | 120.1 | C13—C10—C9 | 118.9 (3) |
C3—C2—C1 | 120.3 (3) | C11—C10—C9 | 123.5 (3) |
C3—C2—H2B | 119.9 | C12—C11—C10 | 118.9 (3) |
C1—C2—H2B | 119.9 | C12—C11—H11A | 120.6 |
C4—C3—C2 | 120.7 (3) | C10—C11—H11A | 120.6 |
C4—C3—H3B | 119.7 | C14—C12—C11 | 118.9 (3) |
C2—C3—H3B | 119.7 | C14—C12—H12A | 120.5 |
C3—C4—C5 | 119.4 (3) | C11—C12—H12A | 120.5 |
C3—C4—H4B | 120.3 | N5—C13—C10 | 124.3 (3) |
C5—C4—H4B | 120.3 | N5—C13—H13A | 117.8 |
C6—C5—C4 | 120.7 (3) | C10—C13—H13A | 117.8 |
C6—C5—H5B | 119.6 | N5—C14—C12 | 123.0 (3) |
C4—C5—H5B | 119.6 | N5—C14—H14A | 118.5 |
C5—C6—C1 | 119.1 (3) | C12—C14—H14A | 118.5 |
C5—C6—C7 | 118.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4A···N5i | 0.86 | 1.96 | 2.823 (4) | 175 |
C7—H7A···S1 | 0.93 | 2.64 | 3.209 (4) | 120 |
C11—H11A···N2 | 0.93 | 2.57 | 2.970 (4) | 106 |
Symmetry code: (i) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C14H11N5S |
Mr | 281.34 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 9.2400 (18), 14.217 (3), 13.302 (4) |
β (°) | 128.408 (19) |
V (Å3) | 1369.3 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.23 |
Crystal size (mm) | 0.20 × 0.15 × 0.11 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3100, 2928, 1176 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.638 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.129, 0.96 |
No. of reflections | 2928 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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).
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4A···N5i | 0.86 | 1.96 | 2.823 (4) | 175 |
C7—H7A···S1 | 0.93 | 2.64 | 3.209 (4) | 120 |
C11—H11A···N2 | 0.93 | 2.57 | 2.970 (4) | 106 |
Symmetry code: (i) −x+1, y+1/2, −z+1/2. |
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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 C═S bond length (1.666 (3) Å) and C7═N2 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.