MOLSTR 10363

Journal of Molecular Structure 470 (1998) 61–69

A structural comparison of some amine- and thione-substituted

triazoles
Ashok K. Sen a, Rajkumar Noren Singh a, Ram N. Handa a, Surendra N. Dubey a,
Philip J. Squattrito b,*
a
Department of Chemistry, Kurukshetra University, Kurukshetra 136119, Haryana, India
b
Department of Chemistry, Central Michigan University, Mt. Pleasant, MI 48859 USA

Received 3 November 1997; revised 15 December 1997; accepted 5 January 1998

Abstract

A series of amine- and thione-substituted triazoles have been synthesized and their structures determined by single-crystal
X-ray diffraction methods. The compounds differ in the identity of the amine- and alkyl-substituents on the triazole ring.
Crystal data for 4-furfuralideneamino-3-methyl-4,5-dihydro-1H-1,2,4-triazole-5-thione, C 8H 8N 4OS: triclinic, space group P1,
3
Z = 2, a = 10:490(2) Å, b = 10:700(2) Å, c = 4:2185(8) Å, a = 92:68(2)⬚, b = 90:17(2)⬚, g = 92:61(1)⬚, V = 472:5(1) Å ,
R(F) = 0:040 for 151 variables and 1056 observations (I ⬎ 3j(I)); 4-furfuralideneamino-3-ethyl-4,5-dihydro-1H-1,2,4-
triazole-5-thione, C 9H 10N 4OS: triclinic, space group P1, Z = 2, a = 8:366(3) Å, b = 9:296(2) Å, c = 7:953(2) Å,
3
a = 113:72(2)⬚, b = 108:54(3)⬚, g = 84:94(3)⬚, V = 536:3(3) Å , R(F) = 0:037 for 136 variables and 1126 observations
(I ⬎ 3j(I)); 4-furfuralideneamino-3-propyl-4,5-dihydro-1H-1,2,4-triazole-5-thione, C 10H 12N 4OS: triclinic, space group P1,
3
Z = 2, a = 9:149(3) Å, b = 9:177(2) Å, c = 8:045(4) Å, a = 110:11(2)⬚, b = 114:52(3)⬚, g = 86:44(2)⬚, V = 574:5(4) Å ,
R(F) = 0:040 for 145 variables and 1414 observations (I ⬎ 3j(I)); 4-(2-acetylpyridyleneamino)-3-ethyl-4,5-dihydro-1H-
1,2,4-triazole-5-thione, C 11H 13N 5S: triclinic, space group P1, Z = 2, a = 7:736(3) Å, b = 11:752(4) Å, c = 7:219(2) Å,
3
a = 93:68(3)⬚, b = 106:26(3) Å, g = 91:04(3)⬚, V = 628:3(4) Å , R(F) = 0:043 for 154 variables and 1224 observations
(I ⬎ 3j(I)). The molecules show substantial variations in conformation as well as in crystal packing. The differences in
molecular structure are discussed in terms of the potential of the molecules to act as bidentate ligands towards metal ions.
䉷 1998 Elsevier Science B.V. All rights reserved.

Keywords: Crystal structure; Triazoles; Amine-substituted triazoles; Thione-substituted triazoles

1. Introduction [1–4]. Molecules that possess an S–C–N–N linkage

can potentially bind to a metal ion in a bidentate fash-
Metal complexes of compounds with S–C–N ion through the S atom and the second N atom. One
linkages display a wide range of biological activity such molecule is 4-amino-3-methyl-4,5-dihydro-1H-
1,2,4-triazole-5-thione [5] which has been found to
coordinate to nickel(II) [6] and copper(I) [7] through
* Corresponding author. Tel.: 001 517 774 3981; Fax: 001 517 774
the amine and thione substituents on the triazole ring.
3883; E-mail: philip.squattrito@cmich.edu
Dedicated with affection and gratitude to Professor Abraham In crystals of the free ligand and its metal complexes,
Clearfield on the occasion of his 70th birthday this triazole exists as the thione tautomer with the H

0022-2860/98/$ - see front matter 䉷 1998 Elsevier Science B.V. All rights reserved.
PII S 00 22 - 28 6 0( 9 8) 0 04 7 0- 0
62 A.K. Sen et al./Journal of Molecular Structure 470 (1998) 61–69

8.0 g of 4-amino-3-methyl-4,5-dihydro-1H-1,2,4-
triazole-5-thione in ethanol. After 2 h of refluxing, a
brown solid began to separate from the solution. The
reaction mixture was cooled and the product isolated
by filtration. The product was recrystallized from
ethanol and light brown crystals of 1 were obtained
with a yield of 75% (m.p., 225⬚C). Analysis (National
Chemical Consulting, Tenafly, NJ): found, C (46.78);
H (3.24); N (28.20); calculated, C (46.14); H (3.87); N
(26.90).

2.2. Synthesis of 3-C 2H 5-4-(C 4H 3O)CHN-5-S-C 2N 3H

(2)

A mixture of 10 g (0.094 mol) of thiocarbohydra-

Scheme 1.
zide in 60 ml of propionic acid was heated under
reflux for 4 h. Within 1 h of refluxing, a pale yellow
atom on the ring N atom adjacent to the thione. As a solid began to separate from the clear solution. The
continuation of this study, we have synthesized and product of this reaction, 4-amino-3-ethyl-4,5-dihydro-
structurally characterized a series of amine- and 1H-1,2,4-triazole-5-thione, was isolated with a 76%
thione-substituted triazoles, shown above in yield, and was recrystallized from water (m.p.,
Scheme 1, that differ in the identity of the alkyl R 148⬚C). The final product, 4-furfuralideneamino-3-
group on the triazole ring and the R⬘ group on the ethyl-4,5-dihydro-1H-1,2,4-triazole-5-thione (2), was
amine substituent. These molecules represent poten- prepared by refluxing an equimolar mixture of
tial ligands for metal complexes that may also be furfuraldehyde and 4-amino-3-ethyl-4,5-dihydro-1H-
biologically active. In this paper we report the crystal 1,2,4-triazole-5-thione in ethanol for 3–4 h. The
and molecular structures of this set of related com- solution was allowed to stand overnight at room
pounds and examine the likelihood of their chelating temperature, during which time pale yellow crystals
metal ions given their observed conformations. of 2 formed. The product was recrystallized from
ethanol (m.p., 190⬚C). Analysis: found, C (48.57); H
(4.05); N (25.24); calculated, C (48.64); H (4.54); N
2. Experimental (25.21).

2.1. Synthesis of 3-CH 3-4-(C 4H 3O)CHN-5-S-C 2N 3H 2.3. Synthesis of 3-C 3H 7-4-(C 4H 3O)CHN-5-S-C 2N 3H
(1) (3)

A mixture of 10 g (0.094 mol) of thiocarbohydra- A mixture of 10 g (0.094 mol) thiocarbohydrazide

zide in 60 ml of glacial acetic acid was heated under in 30 ml of butanoic acid was heated under reflux for
reflux for 4 h. Within 1 h of refluxing, a pale yellow 5–6 h. Within 1 h of refluxing, a cream-colored solid
solid started separating from the clear solution. The started separating from the solution. After the reflux,
reaction mixture was allowed to stand overnight at the excess butanoic acid was distilled off and the
room temperature, and the product of this reaction, remaining liquid was allowed to stand overnight at
4-amino-3-methyl-4,5-dihydro-1H-1,2,4-triazole-5- room temperature. The solid that had crystallized
thione, was isolated with a yield of 80%, and recrys- was filtered, washed with ether and recrystallized
tallized from ethanol (m.p., 204⬚C). The final product, from an equimolar solution of dioxane and water.
4-furfuralideneamino-3-methyl-4,5-dihydro-1H-1,2,- Cream-colored crystals of 4-amino-3-propyl-4,5-
4-triazole-5-thione (1), was prepared by refluxing an dihydro-1H-1,2,4-triazole-5-thione were isolated
equimolar mixture of 5.1 ml of furfuraldehyde and with a 74% yield (m.p., 104⬚C). The final product,
 A.K. Sen et al./Journal of Molecular Structure 470 (1998) 61–69 63

4-furfuralideneamino-3-propyl-4,5-dihydro-1H-1,2,- dispersion terms [11] were from standard sources.

4-triazole-5-thione (3), was prepared by refluxing an Data were corrected for Lorentz and polarization
equimolar mixture of furfuraldehyde and 4-amino- effects. An absorption correction based on w scans
3-propyl-4,5-dihydro-1H-1,2,4-triazole-5-thione in [12] of three reflections was applied to the data of 2.
ethanol for 2–3 h. The solution was concentrated The space group was assigned in each case as P1
and allowed to stand overnight at room temperature based on intensity statistics and the overall likelihood
during which time cream-colored crystals of 3 of the centrosymmetric space group. Successful
formed. The product was recrystallized from ethanol refinements confirmed the space group selection.
(m.p., 155⬚C). Analysis: found, C (49.60); H (4.65); The S atoms were located on E-maps generated by
N, (23.24); calculated, C (50.83); H (5.12); N (23.71). the direct methods program MITHRIL [13], while
the lighter non-hydrogen (O, N and C) atom positions
2.4. Synthesis of 3-C 2H 5-4-(C 5H 4N)C(CH 3)N-5-S- were obtained by difference Fourier methods (DIR-
C 2N 3H (4) DIF [14]). The hydrogen atoms were located on dif-
ference electron density maps following least-squares
An equimolar mixture of 4-amino-3-ethyl-4,5- refinement. The H atom positions of 1 were refined
dihydro-1H-1,2,4-triazole-5-thione and 2-acetylpyri- while those of the other compounds were kept fixed.
dine in dry methanol was refluxed for 6 h. The solu- The B iso value of each H atom was set at 1.2 times the
tion was cooled and kept undisturbed for 5–6 days in B eq value of the attached atom at the time of its inclu-
the refluxing flask. During this time, large colorless sion. Final refinements included anisotropic displace-
block-shaped crystals of 4 were obtained with a 75% ment parameters for all non-hydrogen atoms and were
yield (m.p., 190⬚C). Analysis: found, C (54.53); H performed on those data having I ⬎ 3j(I). There were
(5.05); N 29.04; calculated, C (53.42); H (5.30); N no unusual variations in F o − F c as a function of
(28.32). (sin v)/l, Miller indices, or F o. Crystallographic data
for the four compounds are summarized in Table 1.
2.5. Crystallographic studies Final positional and equivalent isotropic displacement
parameters are listed in Table 2.
All the single-crystal X-ray diffraction measure-
ments were performed at room temperature on a
Rigaku AFC6S four-circle diffractometer (graphite- 3. Results
monochromated 2.0 kW Mo Ka X-ray source;
l = 0:71069 Å) operated by MSC-AFC diffractometer 3.1. 3-CH 3-4-(C 4H 3O)CHN-5-S-C 2N 3H
control software [8]. All crystals were cut from larger
fragments and were mounted on glass fibers with sili- The molecular structure of 1 is shown in Fig. 1 and
cone cement. Unit cell parameters were obtained by a packing diagram with the unit cell outline is pro-
indexing 25 reflections found during a search of reci- vided in Fig. 2. Selected bond distances and angles for
procal space and were refined by a least-squares all four compounds are presented in Table 3. The
analysis of the setting angles of 20–24 high-angle molecule exists in the thione tautomeric form with
reflections (19⬚ ⬍ 2v(Mo Ka) ⬍ 42⬚). Intensity data an S–C distance of 1.681(4) Å which indicates
in the range 3–50⬚2v were collected with q scans of substantial double bond character [5]. All the bond
4⬚ min −1 (1 and 4) or 8⬚ min −1 (2 and 3). Reflections distances and angles of the triazole moiety are
were measured at a constant scan rate with up to four within four estimated standard deviations of those
scans for weaker data (those with I ⬍ 10j(I)). The reported for 4-amino-3-methyl-4,5-dihydro-1H-
intensities of three standard reflections measured 1,2,4-triazole-5-thione [5], except the angles involv-
after every 150 data showed no significant variations ing the amine substituent. The angles in 1 are approxi-
in any of the experiments. All crystallographic calcu- mately 5⬚ larger (C1–N1–N4 = 133:7(3)⬚) and smaller
lations were performed on a VAXStation 3100/76 (C2–N1–N4 = 118:7(3)⬚) than those in the parent
computer with the TEXSAN [9] series of programs. triazole. This distortion may be the result of non-
Atomic scattering factors [10] and anomalous bonded interactions between the S atom and H2, the
64 A.K. Sen et al./Journal of Molecular Structure 470 (1998) 61–69

Table 1
Crystallographic data for new amine- and thione-substituted triazoles

Parameter (1) (2) (3) (4)

Empirical formula C 8H 8N 4OS C 9H 10N 4OS C 10H 12N 4OS C 11H 13N 5S
Formula weight 208.24 222.26 236.29 247.32
Crystal system Triclinic Triclinic Triclinic Triclinic
a (Å) 10.490(2) 8.366(3) 9.149(3) 7.736(3)
b (Å) 10.700(2) 9.296(2) 9.177(2) 11.752(4)
c (Å) 4.2185(8) 7.953(2) 8.045(4) 7.219(2)
a (⬚) 92.68(2) 113.72(2) 110.11(2) 93.69(3)
b (⬚) 90.17(2) 108.54(3) 114.52(3) 106.27(3)
g (⬚) 92.61(1) 84.94(3) 86.44(2) 91.05(3)
V (Å 3) 472.5(1) 536.3(3) 574.5(4) 628.3(4)
Space group P1 (no. 2) P1 (no. 2) P1 (no. 2) P1 (no. 2)
Z value 2 2 2 2
D calc (g cm −3) 1.464 1.376 1.366 1.307
F(000) 216 232 248 260
m (cm −1) 2.99 2.68 2.54 2.32
Transmission factors None 0.93–1.00 None None
2v range for data (⬚) 3–50 3–50 3–50 3–50
Data collected + h, ⫾ k, ⫾ l + h, ⫾ k, ⫾ l + h, ⫾ k, ⫾ l + h, ⫾ k, ⫾ l
Total data 1738 2012 2151 2386
Number of unique data 1640 1874 2012 2206
R int 0.034 0.014 0.012 0.030
Number of data I ⬎ 3j(I) 1056 1126 1414 1224
Number of variables 151 136 145 154
R F†; R w F† (I ⬎ 3j I†) 0.040; 0.039 0.037; 0.036 0.040; 0.039 0.043; 0.040
Goodness of fit 2.05 2.00 2.43 2.10
Peaks in final DF (e − Å −3) 0.27, − 0.19 0.17, − 0.16 0.20, − 0.25 0.18, − 0.25

latter of which is not present in the parent. Overall, the

molecule is fairly flat, with a dihedral angle of 14.3⬚
between the essentially planar triazole and furfurali-
dene rings. The torsion angle C1–N1–N4–C3 is 11.2⬚
so that the furfuralidene group is rotated towards the
viewer relative to the triazole ring. The packing diagram

Fig. 1. ORTEP diagram of the molecular structure of 1 showing the

atom labelling scheme. In this and subsequent figures, the displace-
ment ellipsoids are shown at the 50% probability level except for Fig. 2. ORTEP packing diagram of 1 showing the outline of the unit
those of the hydrogen atoms, which are shown as spheres of arbi- cell. View is approximately along the c axis. The S, O and N atoms
trary size. are shown with octant shading.
 A.K. Sen et al./Journal of Molecular Structure 470 (1998) 61–69 65

Table 2 Table 2 Continued

Fractional atomic coordinates and equivalent isotropic displace-
ment parameters Atom x y z B eq a

Atom x y z B eq a 3-C 2H 5-4-(C 5H 4N)C(CH 3)N-5-S-C 2N 3H

S 0.7420(2) 0.1289(1) 0.0544(2) 4.61(5)
3-CH 3-4-(C 4H 3O)CHN-5-S-C 2N 3H N1 0.6070(4) 0.1958(3) − 0.3145(4) 3.4(1)
S 0.6749(1) 0.49327(9) 0.3475(3) 4.15(5) N2 0.4462(4) 0.0654(3) − 0.2485(5) 3.7(1)
O 0.9771(2) 0.8610(2) 1.0232(6) 3.9(1) N3 0.3592(4) 0.0901(3) − 0.4341(5) 3.6(1)
N1 0.6893(3) 0.7540(3) 0.3970(7) 3.0(1) N4 0.7294(4) 0.2904(3) − 0.2944(5) 3.8(1)
N2 0.5414(3) 0.6746(3) 0.0957(8) 3.7(2) N5 1.1854(4) 0.3381(3) − 0.2674(5) 4.7(2)
N3 0.5309(3) 0.8027(3) 0.0841(7) 3.6(1) C1 0.5981(5) 0.1289(3) − 0.1682(5) 3.3(2)
N4 0.7875(3) 0.7871(3) 0.6089(7) 3.1(1) C2 0.4580(5) 0.1720(3) − 0.4703(6) 3.5(2)
C1 0.6356(3) 0.6402(3) 0.2794(8) 3.2(2) C3 0.8857(5) 0.2639(3) − 0.3042(5) 3.2(2)
C2 0.6225(3) 0.8475(3) 0.2683(9) 3.3(2) C4 0.4227(5) 0.2341(4) − 0.6471(6) 4.7(2)
C3 0.8616(3) 0.7046(4) 0.6999(9) 3.3(2) C5 0.2510(6) 0.1954(4) − 0.7932(7) 7.0(3)
C4 0.9652(3) 0.7392(3) 0.9101(9) 3.0(2) C6 0.9490(5) 0.1478(3) − 0.3386(6) 4.6(2)
C5 1.0636(4) 0.6764(4) 1.017(1) 4.4(2) C7 1.0171(5) 0.3635(3) − 0.2730(5) 3.3(2)
C6 1.1417(4) 0.7612(4) 1.203(1) 4.6(2) C8 0.9636(5) 0.4738(4) − 0.2525(6) 4.6(2)
C7 1.0866(4) 0.8707(4) 1.200(1) 4.4(2) C9 1.0942(7) 0.5627(4) − 0.2159(7) 5.6(2)
C8 0.6559(4) 0.9823(4) 0.334(1) 4.0(2) C10 1.2671(6) 0.5374(4) − 0.2051(7) 5.4(2)
C11 1.3083(5) 0.4250(4) − 0.2343(7) 5.6(2)
3-C 2H 5-4-(C 4H 3O)CHN-5-S-C 2N 3H
S 0.2998(1) 0.2944(1) 0.3265(1) 5.00(4)
O 0.1394(3) − 0.2303(3) 0.4243(3) 5.0(1)
a
Beq = (4=3)[a2 b11 + b2 b22 + c2 b33 + (2ab cos g)b12 + (2ac cos b) ×
N1 0.4081(3) 0.1902(3) 0.6261(3) 3.1(1) b13 + (2bc cos a)b23 ]
N2 0.5301(3) 0.4015(3) 0.6812(4) 4.2(1)
N3 0.6046(3) 0.3705(3) 0.8438(4) 4.1(1)
N4 0.3207(3) 0.0461(3) 0.5550(4) 3.5(1) shows that the molecules are arranged in staggered rows
C1 0.4111(4) 0.2945(4) 0.5436(4) 3.6(1) running parallel to the a axis with the molecules in
C2 0.5286(4) 0.2407(4) 0.8070(4) 3.4(1) adjacent rows in opposite orientations. The main inter-
C3 0.1866(4) 0.0162(4) 0.4118(5) 3.7(1) molecular interaction is a hydrogen bond between H1
C4 0.0911(4) − 0.1297(4) 0.3337(4) 3.4(1)
and S (N2–H1…S, 0.97(3); 2.37(3) Å; 173(3)⬚) on each
C5 − 0.0467(4) − 0.1909(4) 0.1784(5) 4.6(1)
C6 − 0.0869(5) − 0.3382(4) 0.1709(5) 5.3(2) side of the center of inversion.
C7 0.0261(5) − 0.3564(4) 0.3199(6) 5.8(2)
C8 0.5598(4) 0.1562(4) 0.9369(5) 4.3(1)
C9 0.7105(5) 0.2228(5) 1.1130(5) 5.9(2)
3.2. 3-C 2H 5-4-(C 4H 3O)CHN-5-S-C 2N 3H

3-C 3H 7-4-(C 4H 3O)CHN-5-S-C 2N 3H The molecular structure of 2 is depicted in Fig. 3,

S 0.7201(1) 0.1879(1) 0.6819(1) 4.32(3) while a packing diagram and unit cell outline are
O 1.2500(2) 0.3453(3) 0.5985(3) 5.24(9) shown in Fig. 4. The bond distances and angles in
N1 0.8120(3) 0.0898(2) 0.3744(3) 2.98(8)
N2 0.5981(3) − 0.0318(3) 0.3194(3) 3.66(9)
the triazole moiety (Table 3) are not substantially dif-
N3 0.6224(3) − 0.0981(3) 0.1520(3) 3.9(1) ferent from those in 1; however the conformation of
N4 0.9624(3) 0.1738(3) 0.4510(3) 3.30(9) the molecule is different. The dihedral angle of 13.3⬚
C1 0.7101(3) 0.0822(3) 0.4589(4) 3.1(1) between the triazole and furfuralidene rings is similar
C2 0.7545(3) − 0.0229(3) 0.1897(4) 3.3(1) to that in 1, indicating that 2 is also approximately
C3 0.9837(3) 0.3096(3) 0.5761(4) 3.4(1)
C4 1.1335(3) 0.4045(3) 0.6581(4) 3.2(1)
planar; however, the furfuralidene ring is rotated
C5 1.1842(4) 0.5500(3) 0.7898(4) 4.6(1) in the opposite direction to 1, away from the
C6 1.3415(4) 0.5849(4) 0.8136(5) 4.9(1) viewer relative to the triazole (torsion angle
C7 1.3759(4) 0.4610(4) 0.6976(6) 6.2(2) C1–N1–N4–C3 = − 22:3⬚). The molecules also pack
C8 0.8349(4) − 0.0431(3) 0.0567(4) 4.3(1) differently. As in 1, there are staggered rows of
C9 0.7573(4) − 0.1787(4) − 0.1373(4) 4.7(1)
C10 0.7876(4) − 0.3345(4) − 0.1163(5) 5.7(1)
molecules, in this case running parallel to the c axis,
with adjacent rows related by the center of inversion.
The molecules in 2 are standing upright in their rows
66 A.K. Sen et al./Journal of Molecular Structure 470 (1998) 61–69

Fig. 3. ORTEP diagram of the molecular structure of 2 showing the

Fig. 4. ORTEP packing diagram of 2 showing the outline of the unit
atom labelling scheme.
cell. View is approximately along the a axis. The S, O and N atoms
are shown with octant shading.
while those in 1 are lying on their sides. Despite the
different orientations, the N2–H1…S hydrogen bond- consistent with those in 1 and 2, although a small
ing interaction is preserved in 2 (1.02; 2.30 Å; 172⬚). but significant lengthening of the N1–N4 bond and
contraction of the N1–N4–C3 angle are evident in
3.3. 3-C 3H 7-4-(C 4H 3O)CHN-5-S-C 2N 3H Table 3. As was the case with 1 and 2, the most sub-
stantial change is in the conformation of the molecule.
The molecular structure of 3 appears in Fig. 5, and a There is a much larger deviation from coplanarity
packing diagram with unit cell outline is present in between the rings (dihedral angle, 30.5⬚) and the
Fig. 6. The bond distances and angles are mostly furfuralidene moiety is rotated further away from

Table 3
Selected bond distances (Å), bond angles (⬚), and torsion angles (⬚)

(1) (2) (3) (4)

S–C1 1.681(4) 1.681(3) 1.687(3) 1.679(4)

N1–C1 1.387(4) 1.377(4) 1.379(3) 1.372(4)
N1–N4 1.385(3) 1.396(3) 1.403(3) 1.420(4)
N1–C2 1.379(4) 1.388(4) 1.385(3) 1.376(4)
N3–C2 1.295(4) 1.296(4) 1.297(3) 1.303(4)
N2–N3 1.383(4) 1.378(3) 1.379(3) 1.373(4)
N2–C1 1.330(4) 1.335(4) 1.332(3) 1.343(4)
N4–C3 1.273(4) 1.274(4) 1.268(3) 1.274(4)
S–C1–N1 130.1(3) 131.1(2) 129.9(2) 128.0(3)
S–C1–N2 127.0(3) 126.6(2) 127.4(2) 129.6(3)
N3–N2–C1 114.6(3) 114.4(2) 114.3(2) 113.8(3)
N2–N3–C2 103.1(3) 104.1(2) 104.1(2) 104.5(3)
N1–C2–N3 111.9(3) 110.3(3) 110.5(2) 109.9(3)
C1–N1–C2 107.6(3) 108.8(2) 108.5(2) 109.3(3)
N4–N1–C2 118.7(3) 118.7(2) 119.4(2) 124.6(3)
N4–N1–C1 133.7(3) 132.2(3) 131.6(2) 124.9(3)
N1–C1–N2 102.8(3) 102.4(3) 102.7(2) 102.4(3)
N1–N4–C3 120.2(3) 118.3(3) 117.0(2) 114.4(3)
C1–N1–N4–C3 11.2(5) − 22.3(5) − 36.5(4) 82.3(5)
C2–N1–N4–C3 − 170.8(3) 164.6(3) 153.0(3) − 111.5(4)
 A.K. Sen et al./Journal of Molecular Structure 470 (1998) 61–69 67

Fig. 5. ORTEP diagram of the molecular structure of 3 showing the

atom labelling scheme.

the viewer than in 2 (torsion angle

C1–N1–N4–C3 = − 36:5⬚). The positioning of the
propyl group results in a further deviation from over-
all planarity for 3 compared to 1 and 2. The molecules
of 3 pack in a manner similar to 1, with adjacent rows
of molecules on their sides (running parallel to the b
axis) related by the center of inversion. The same Fig. 6. ORTEP packing diagram of 3 showing the outline of the unit
intermolecular hydrogen bonding interaction is pre- cell. The view is approximately onto the [101] plane. The S, O and
sent in 3 (N2–H1…S, 1.00; 2.34 Å; 165⬚). N atoms are shown with octant shading.

approximately perpendicular to one another. The non-

3.4. 3-C 2H 5-4-(C 5H 4N)C(CH 3)N-5-S-C 2N 3H planarity of the molecule and the presence of the
pyridine ring affect the crystal packing as well. As
The molecular structure of 4 is shown in Fig. 7, in 1–3 there are rows of molecules, in this case
while a packing diagram and unit cell outline appears
in Fig. 8. This molecule carries an ethyl group on the
triazole ring as does 2, but differs from the other
molecules in having the 2-acetylpyridylene group on
the amine in place of the furfuralidene group. This
molecule shows some significant structural differ-
ences from the other members of the series, most
notably a longer N1–N4 bond, nearly equal C2–
N1–N4 and C1–N1–N4 bond angles, and a smaller
N1–N4–C3 bond angle. Presumably these differences
arise from the presence of the methyl group on C3
instead of a hydrogen atom. The torsion angle C1–
N1–N4–N3 is 82.3⬚ and the dihedral angle between
the rings is 107.4⬚ indicating that in order to avoid
steric interactions between the methyl group of the
2-acetylpyridylene and either the S atom or the ethyl Fig. 7. ORTEP diagram of the molecular structure of 4 showing the
group of the triazole, the two parts of the molecule are atom labelling scheme.
68 A.K. Sen et al./Journal of Molecular Structure 470 (1998) 61–69

contacts between the H atoms on C3 (or C6 in 4)

and those on the R group attached to C2. Other
S–C–N–N–R⬘ compounds have been observed to
bind to metal ions in either a monodentate fashion
through S [16] or in the desired chelating S, N
arrangement [17], [18]. In the former case, the R⬘
group is positioned as in 1–4, while in the latter
cases, 2-acetylpyridine [17] and 2-formylpyridine
[18] thiosemicarbazones, the pyridine N atom also
coordinates to the metal making the ligand tridentate.
These molecules adopt conformations as free ligands
which have the coordinating amine N atom and thione
Fig. 8. ORTEP packing diagram of 4 showing the outline of the unit
cell. View is approximately along the c axis. The S and N atoms are S atom trans to one another across the C–N bond.
shown with octant shading. Whether a similar coordination mode is possible for
4 remains to be determined. The ability of the mole-
cules in this study to adopt conformations more favor-
running parallel to the a axis, with adjacent rows able to metal chelation depends in part on the ease of
inverted. In 4 the rows are interleaved so as to afford rotation about the N1–N4 bond. This bond is longer
a face-to-face contact between the pyridine rings (1.385(3)–1.420(4) Å) than the correspoding bond in
about the center of inversion. This type of interaction the heterocyclic thiosemicarbazones (1.375(2) and
is not observed in the furfuralidene derivatives. The 1.370(2) Å) [18]. Alternatively, replacing the R
triazole moieties are arranged so that the N2–H1…S group with H, or choosing R and R⬘ groups capable
hydrogen bonds are preserved (1.10; 2.20 Å; 166⬚). of forming intramolecular hydrogen bonds might
result in greater stability for the conformation which
places the lone pair of the amine N atom adjacent to
4. Discussion the S atom, thus leading to greater likelihood of
chelation. Experiments to test these ideas using reac-
Previously we [6], [15] and others [7] have found tion conditions, such as acidic media [19], which have
that 4-amine-3-methyl-4,5-dihydro-1H-1,2,4-triazole- been successful in related systems, are underway.
5-thione forms bidentate complexes with the divalent
first row transition metals Mn–Zn, coordinating to the
metal ion via the thione and amine substituents on the 5. Supplementary material
triazole ring. It is of interest to examine the coordina-
tion chemistry of larger triazole derivatives, such as Hydrogen atom positions and complete tables of
the four molecules in this study, that have organic bond distances and angles have been deposited with
functional groups on the amine N atom. Initial efforts the Cambridge Crystallographic Data Centre, 12
to obtain crystals of the metal complexes suitable for Union Road, Cambridge CB2 1EZ, UK. Additional
structural studies have not been successful. One crystallographic data can be obtained from the authors
reason may be that in each case the conformation (P.J.S.).
adopted by the free ligand in the solid state places
the organic group attached to N4 on the same side
of the N1–N4 bond as the S atom. Thus the C3 Acknowledgements
atom is blocking N4 from chelating a metal ion
together with the S atom. If this is also the dominant The support of the Herbert H. and Grace A. Dow
conformation of these molecules in solution, it would Foundation, the Dow Chemical Company Foundation
help to explain the apparent tendency not to bind and Central Michigan University in the establishment
strongly to form metal chelates. This conformation of the CMU X-ray Crystallography Laboratory is
presumably occurs, in part, to avoid non-bonded gratefully acknowledged.
 A.K. Sen et al./Journal of Molecular Structure 470 (1998) 61–69 69

References [11] D. Cromer, International Tables for X-ray Crystallography,

Vol. IV, Kynoch Press, Birmingham, UK, 1974, Table 2.3.1.
[1] O.E. Offiong, Transition Met. Chem. 20 (1995) 126–131. [12] A.C.T. North, D.C. Phillips, F.S. Mathews, Acta Crystallogr.,
[2] D.X. West, M.A. Lockwood, A.E. Liberta, X. Chen, R.D. Sect. A 24 (1968) 351–359.
Willett, Transition Met. Chem. 18 (1993) 221–227. [13] C. Gilmore, MITHRIL: A Computer Program for the Auto-
[3] K.C. Satpathy, A.K. Panda, R. Mishra, A.P. Chopdar, S.K. matic Solution of Crystal Structures from X-ray Data, Depart-
Pradhan, Transition Met. Chem. 16 (1991) 628–630. ment of Chemistry, University of Glasgow, Scotland, 1983.
[4] D. Kovala-Demertzi, A. Domopoulou, M.A. Demertzis, A. [14] P. Beurskens, DIRDIF: Direct methods for difference struc-
Papageorgiou, D.X. West, Polyhedron 16 (1997) 3625–3633. tures, an automatic procedure for phase extension and refine-
[5] J.L. Escobar-Valderrama, J.H. Garcia-Tapia, J. Ramirez-Ortiz, ment of difference structure factors, Tech. Rep. 1984/1,
M.J. Rosales, R.A. Toscano, J. Valdes-Martinez, Can. J. Crystallography Laboratory, Toernooiveld, 6525 ED Nijme-
Chem. 67 (1989) 198–201. gen, The Netherlands, 1984.
[6] A.K. Sen, S.N. Dubey, P.J. Squattrito, Acta Crystallogr., Sect. [15] R.W. Clark, P.J. Squattrito, A.K. Sen, S.N. Dubey, unpub-
C 52 (1996) 865–868. lished results.
[7] M.B. Cingi, F. Bigoli, M. Lanfranchi, E. Leporati, M.A. [16] H. Zheng, D. Zeng, X. Xin, W. Wong, Polyhedron 16 (1997)
Pellinghelli, C. Foglia, Inorg. Chim. Acta 235 (1995) 37–43. 3499–3503.
[8] MSC/AFC Diffractometer Control Software, Version 4.2.0, [17] D.X. West, I.S. Billeh, G.A. Bain, J. Valdes-Martinez, K.H.
Molecular Structure Corporation, The Woodlands, TX, USA, Ebert, S. Hernandez-Ortega, Transition Met. Chem. 21 (1996)
1988. 573–582.
[9] TEXSAN, Texray Structural Analysis Package, Version 5.0, [18] D.X. West, G.A. Bain, R.J. Butcher, J.P. Jasinski, Y. Li, R.Y.
Molecular Structure Corporation, The Woodlands, TX, USA, Pozdniakiv, J. Valdes-Martinez, R.A. Toscano, S. Hernandez-
1991. Ortega, Polyhedron 15 (1996) 665–674.
[10] D. Cromer, J. Waber, International Tables for X-ray Crystal- [19] D. Chattopadhyay, S.K. Majumdar, P. Lowe, C.H. Schwalbe,
lography, Vol. IV, Kynoch Press, Birmingham, UK, 1974, S.K. Chattopadhyay, S. Ghosh, J. Chem. Soc., Dalton Trans.
Table 2.2A. (1991) 2121–2124.