organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

2-Amino-5-tri­fluoro­methyl-1,3,4-thia­diazole and a redetermination of 2-amino-1,3,4-thia­diazole, both at 120 K: chains of edge-fused R22(8) and R44(10) rings, and sheets of R22(8) and R66(20) rings

CROSSMARK_Color_square_no_text.svg

aComplexo Tecnológico de Medicamentos Farmanguinhos, Avenida Comandante Guaranys 47, Jacarepaguá, Rio de Janeiro, RJ, Brazil, bDepartamento de Química Orgânica, Instituto de Química, Universidade Federal do Rio de Janeiro, CEP 21945-970, Rio de Janeiro, RJ, Brazil, cSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland, and dDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland
*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 30 November 2005; accepted 1 December 2005; online 24 December 2005)

Mol­ecules of 2-amino-5-trifluoro­methyl-1,3,4-thia­diazole, C3H2F3N3S, are linked by two independent N—H⋯N hydrogen bonds into sheets of alternating R22(8) and R66(20) rings, while the mol­ecules of the unsubstituted 2-amino-1,3,4-thia­diazole, C2H3N3S, are linked, again by two independent N—H⋯N hydrogen bonds, but into chains of edge-fused R22(8) and R44(10) rings.

Comment

The structure of 2-amino-1,3,4-thia­diazole, (I)[link], was reported several years ago (Khusenov et al., 1997[Khusenov, K. S., Umarov, B. B., Ishankhodzhaeva, M. M., Parpiev, N. A., Talipov, S. A. & Ibragimov, B. T. (1997). Russ. J. Coord. Chem. 23, 555-559; Chem. Abstr. 127, 302376x.]). The use of room-temperature diffraction data gave a final R value of 0.079, but no H-atom coordinates were reported, so that it is not possible fully to analyse the supramolecular aggregation. We have now reinvestigated this compound using diffraction data collected

[Scheme 1]
at 120 K, together with the substituted analogue 2-amino-5-trifluoro­methyl-1,3,4-thia­diazole, (II)[link], which is itself closely related to both 2-amino-5-methyl-1,3,4-thia­diazole, (III)[link] (Lynch, 2001[Lynch, D. E. (2001). Acta Cryst. C57, 1201-1203.]), and 5-amino-3-trifluoro­methyl-1H-1,2,4-triazole, (IV)[link] (Borbulevych et al., 1998[Borbulevych, O. Y., Shishkin, O. V., Desenko, S. M., Chernenko, V. N. & Orlov, V. D. (1998). Acta Cryst. C54, 442-444.]; Boechat et al., 2004[Boechat, N., Dutra, K. D. B., Valverde, A. L., Wardell, S. M. S. V., Low, J. N. & Glidewell, C. (2004). Acta Cryst. C60, o733-o736.]).

Within the mol­ecules of (I)[link] and (II)[link] (Figs. 1[link] and 2[link]), the corresponding bond distances (Table 1[link]) are fairly similar, and they show no real evidence for aromatic type π-electron delocalization. In particular, the C—S distances are all much longer than such bonds in thio­phenes (Allen et al., 1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]). In each of (I)[link] and (II)[link], the C—S—C angle is less than 90°, with compensatory larger angles elsewhere in the rings (Table 1[link]).

In each of (I)[link] and (II)[link], the amino groups act as double donors in N—H⋯N hydrogen bonds (Tables 2[link] and 3[link]). However, in (I)[link], the resulting supramolecular structure is one-dimensional, while in (II)[link] it is two-dimensional. In compound (I)[link], amino atom N2 in the mol­ecule at (x, y, z) acts as hydrogen-bond donor, via atoms H21 and H22, respectively, to atoms N3 at (1 − x, 1 − y, 1 − z) and atom N4 at (x, y, −1 + z). Propagation by inversion and translation of these two inter­actions generates a chain of edge-fused rings running parallel to the [001] direction, with R22(8) (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) rings centred at ([{1 \over 2}], [{1 \over 2}], n + [{1 \over 2}]) (n = zero or integer) and R44(10) rings centred at ([{1 \over 2}], [{1 \over 2}], n) (n = zero or integer) (Fig. 3[link]).

The mol­ecules of compound (II)[link] are also linked into centrosymmetric R22(8) dimers (Fig. 4[link]) by paired N—H⋯N hydrogen bonds (Table 3[link]), exactly the same as those in compound (I)[link]. However, the further linking of these dimers generates a (100) sheet, rather than an [001] chain. Amino atoms N2 in the mol­ecules at (x, y, z) and (1 − x, 1 − y, 1 − z), components of the R22(8) dimer centred at ([{1\over 2}], [{1\over 2}], [{1\over 2}]), act as hydrogen-bond donors, via atom H21, to ring atoms N4 in the mol­ecules at (x, [{1\over 2}] − y, [{1\over 2}] + z) and (1 − x, [{1\over 2}] + y, [{1\over 2}] − z), respectively, which are components of the R22(8) dimers centred at ([{1\over 2}], 0, 1) and ([{1\over 2}], 1, 0), respectively. Similarly, atoms N4 in the mol­ecules at (x, y, z) and (1 − x, 1 − y, 1 − z) accept hydrogen bonds from atom N2 in the mol­ecules at (x, [{1\over 2}] − y, −[{1\over 2}] + z) and (1 − x, [{1\over 2}] + y, [{3\over 2}] − z), respectively, which are themselves components of the dimers centred at ([{1\over 2}], 0, 0) and ([{1\over 2}], 1, 1). Propagation of these two hydrogen bonds then generates a (100) sheet in the form of a (6,3)-net (Batten & Robson, 1998[Batten, S. R. & Robson, R. (1998). Angew. Chem. Int. Ed. 37, 1460-1494.]) built from alternating R22(8) and R66(20) rings (Fig. 5[link]).

Thus, the modes of supramolecular aggregation in (I)[link] and (II)[link] are entirely different from one another. In addition, they differ from that in the related triazole, compound (IV), where only two of the three available N—H bonds participate in the aggregation to form a C(4)C(5)[R22(7)] chain of rings (Boechat et al., 2004[Boechat, N., Dutra, K. D. B., Valverde, A. L., Wardell, S. M. S. V., Low, J. N. & Glidewell, C. (2004). Acta Cryst. C60, o733-o736.]). However, compounds (II)[link] and (III)[link] are nearly isostructural, when due account is taken of the space-group settings employed, P21/c for compound (II)[link] reported here and P21/n for (III)[link] reported by Lynch (2001[Lynch, D. E. (2001). Acta Cryst. C57, 1201-1203.]). Both compounds form sheets of alternating R22(8) and R66(20) rings, so that the description of the supramolecular aggregation in (III)[link] as three-dimensional (Lynch, 2001[Lynch, D. E. (2001). Acta Cryst. C57, 1201-1203.]) is, in fact, incorrect.

[Figure 1]
Figure 1
The mol­ecule of compound (I)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2]
Figure 2
The mol­ecule of compound (II)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3]
Figure 3
Part of the crystal structure of compound (I)[link], showing the formation of an [001] chain of edge-fused R22(8) and R44(10) rings. For the sake of clarity, the H atom bonded to atom C5 has been omitted. Atoms marked with an asterisk (*), a hash (#), a dollar sign ($), an ampersand (&) or an `at' sign (@) are at the symmetry positions (1 − x, 1 − y, 1 − z), (x, y, −1 + z), (1 − x, 1 − y, −z), (x, y, 1 + z) and (1 − x, 1 − y, 2 − z), respectively.
[Figure 4]
Figure 4
Part of the crystal structure of compound (II)[link], showing the formation of a centrosymmetric R22(8) dimer. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).
[Figure 5]
Figure 5
A stereoview of part of the crystal structure of compound (II)[link], showing the formation of a (100) sheet of alternating R22(8) and R66(20) rings.

Experimental

To a mixture of equimolar quanti­ties (75 mmol of each) of the thio­semicarbazide H2NCSNHNH2 and the appropriate carboxylic acid RCO2H (R = H or CF3), sulfuric acid (49 mmol) was added dropwise at ambient temperature. The reaction mixtures were then heated at 373 K for 7–10 h with stirring, cooled, poured onto ice–water and rendered alkaline with aqueous sodium hydroxide solution. The resulting solid products were collected by filtration, washed with water, dried and recrystallized from ethanol, to yield crystals of compounds (I)[link] and (II)[link] suitable for single-crystal X-ray diffraction. Analysis for (I)[link]: 10 h reaction, 74% yield, m.p. 464–465 K; 1H NMR (MeOD): δ 7.06 (s, 1H), 8.54 (s, 2H, NH2); 13C NMR (MeOD): δ 144.8 (C1), 171.2 (C2); IR (KBr, ν, cm−1): 3286 and 3091 (N—H), 1618 (C=N), 1509 (NH2), 1021 (C=S). Analysis for (II)[link]: 7 h reaction, 85% yield, m.p. 489–491 K; 1H NMR (MeOD): δ 7.71 (s, NH2); 13C NMR (MeOD: δ 121.1 (q, CF3, J = 269 Hz), 146.8 (q, C2, J = 38 Hz), 173.8 (C1); 19F NMR (MeOD): δ −61.45 (CF3); IR (KBr, ν, cm−1): 3303 and 3127 (N—H), 1640 (C=N), 1519 (NH2), 1075 (C=S), 1193 and 745 (CF3).

Compound (I)[link]

Crystal data
  • C2H3N3S

  • Mr = 101.13

  • Monoclinic, P 21 /n

  • a = 5.5718 (5) Å

  • b = 13.4573 (17) Å

  • c = 5.7875 (5) Å

  • β = 109.984 (6)°

  • V = 407.83 (7) Å3

  • Z = 4

  • Dx = 1.647 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 936 reflections

  • θ = 3.0–27.6°

  • μ = 0.60 mm−1

  • T = 120 (2) K

  • Needle, colourless

  • 0.15 × 0.04 × 0.02 mm

Data collection
  • Nonius KappaCCD area-detector diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.])Tmin = 0.919, Tmax = 0.988

  • 6842 measured reflections

  • 936 independent reflections

  • 736 reflections with I > 2σ(I)

  • Rint = 0.096

  • θmax = 27.6°

  • h = −7 → 7

  • k = −17 → 17

  • l = −6 → 7

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.038

  • wR(F2) = 0.102

  • S = 1.08

  • 936 reflections

  • 59 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.056P)2] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 0.39 e Å−3

  • Δρmin = −0.38 e Å−3

Table 1
Selected geometric parameters (Å, °) for compounds (I)[link] and (II)[link]

  (I)[link] (II)[link]
S1—C2 1.745 (2) 1.749 (2)
C2—N3 1.323 (2) 1.328 (3)
N3—N4 1.390 (2) 1.378 (3)
N4—C5 1.293 (3) 1.291 (3)
C5—S1 1.735 (2) 1.727 (2)
C2—N2 1.345 (3) 1.325 (3)
C5—C51   1.494 (4)
     
C5—S1—C2  86.59 (10)  86.31 (11)
S1—C2—N3 113.86 (15) 113.56 (18)
C2—N3—N4 111.73 (16) 111.81 (19)
N3—N4—C5 113.04 (16) 113.03 (19)
N4—C5—S1 114.78 (16) 115.29 (19)
S1—C2—N2 121.89 (14) 122.35 (17)
N3—C2—N2 124.25 (19) 124.1 (2)

Compound (II)[link]

Crystal data
  • C3H2F3N3S

  • Mr = 169.14

  • Monoclinic, P 21 /c

  • a = 9.1082 (12) Å

  • b = 6.9373 (10) Å

  • c = 10.8048 (14) Å

  • β = 116.656 (9)°

  • V = 610.15 (14) Å3

  • Z = 4

  • Dx = 1.841 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 1386 reflections

  • θ = 3.6–27.5°

  • μ = 0.51 mm−1

  • T = 120 (2) K

  • Plate, colourless

  • 0.32 × 0.24 × 0.06 mm

Data collection
  • Nonius KappaCCD area-detector diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.])Tmin = 0.853, Tmax = 0.970

  • 6231 measured reflections

  • 1386 independent reflections

  • 1093 reflections with I > 2σ(I)

  • Rint = 0.044

  • θmax = 27.5°

  • h = −11 → 11

  • k = −9 → 9

  • l = −14 → 13

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.045

  • wR(F2) = 0.113

  • S = 1.10

  • 1386 reflections

  • 91 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0491P)2 + 0.4024P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.33 e Å−3

  • Δρmin = −0.35 e Å−3

Table 2
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H21⋯N3i 0.87 2.13 2.999 (3) 175
N2—H22⋯N4ii 0.89 2.08 2.969 (2) 172
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, y, z-1.

Table 3
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H21⋯N3i 0.84 2.16 2.985 (3) 171
N2—H22⋯N4ii 0.87 2.10 2.959 (3) 169
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) [x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}].

The space groups P21/n and P21/c for compounds (I)[link] and (II)[link], respectively, were uniquely assigned from the systematic absences. All H atoms were located in difference maps. The coordinates of the H atom bonded to carbon in compound (I)[link] were freely refined, giving a C—H distance of 0.95 (3) Å. H atoms bonded to nitrogen were allowed to ride at the positions found from the difference maps, with Uiso(H) = 1.2Ueq(N); the resulting N—H distances were in the range 0.84–0.89 Å. In (II)[link], the anisotropic displacement parameters for the F atoms suggest that there may be some libration of the CF3 group about the C5—C51 bond.

For both compounds, data collection: COLLECT (Nonius, 1999[Nonius (1999). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]) and SIR92 (Altomare et al., 1993[Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343-350.]); program(s) used to refine structure: OSCAIL (McArdle, 2003[McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.]) and SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information


Comment top

The structure of 2-amino-1,3,4-thiadiazole, (I), was reported several years ago (Khusenov et al., 1997). The use of room-temperature diffraction data gave a final R of 0.079, but no H-atom coordinates were reported, so that it is not possible fully to analyse the supramolecular aggregation. We have now reinvestigated this compound using diffraction data collected at 120 K, together with the substituted analogue 2-amino-5-trifluoromethyl-1,3,4-thiadiazole, (II), which is itself closely related to both 2-amino-5-methyl-1,3,4-thiadiazole, (III) (Lynch, 2001), and 5-amino-3-trifluoromethyl-1H-1,2,4-triazole, (IV) (Borbulevych et al., 1998; Boechat et al., 2004).

Within the molecules of (I) and (II) (Figs. 1 and 2), the corresponding bond distances (Table 1) are fairly similar, and they show no real evidence for aromatic type π-electron delocalization. In particular, the C—S distances are all much longer than such bonds in thiophenes (Allen et al., 1987). In each of (I) and (II), the C—S—C angle is less than 90°, with compensatory larger angles elsewhere in the rings (Table 1).

In each of (I) and (II), the amino groups act as double donors in N—H···N hydrogen bonds (Tables 2 and 3). However, in (I), the resulting supramolecular structure is one-dimensional, while in (II) it is two-dimensional. In compound (I), the amino atom N2 in the molecule at (x, y, z) acts as hydrogen-bond donor, via atoms H21 and H22, respectively, to atoms N at (1 - x, 1 - y, 1 - z) and atom N4 at (x, y, -1 + z). Propagation by inversion and translation of these two interactions generates a chain of edge-fused rings running parallel to the [001] direction, with R22(8) (Bernstein et al., 1995) rings centred at (1/2, 1/2, n + 1/2) (n = zero or integer) and R44(10) rings centred at (1/2, 1/2, n) (n = zero or integer) (Fig. 3).

The molecules of compound (II) are also linked into centrosymmetric R22(8) dimers (Fig. 4) by paired N—H···N hydrogen bonds (Table 3), exactly the same as those in compound (I). However, the further linking of these dimers generates a (100) sheet, rather than an [001] chain. The amino atoms N2 in the molecules at (x, y, z) and (1 - x, 1 - y, 1 - z), components of the R22(8) dimer centred at (1/2, 1/2, 1/2), act as hydrogen-bond donors, via atom H21, to the ring atoms N4 in the molecules at (x, 1/2 - y, 1/2 + z) and (1 - x, 1/2 + y, 1/2 - z), respectively, which are components of the R22(8) dimers centred at (1/2, 0, 1) and (1/2, 1, 0), respectively. Similarly, atoms N4 in the molecules at (x, y, z) and (1 - x, 1 - y, 1 - z) accept hydrogen bonds from atom N2 in the molecules at (x, 1/2 - y, -1/2 + z) and (1 - x, 1/2 + y, 3/2 - z), respectively, which are themselves components of the dimers centred at (1/2, 0, 0) and (1/2, 1, 1). Propagation of these two hydrogen bonds then generates a (100) sheet in the form of a (6,3) net (Batten & Robson, 1998) built from alternating R22(8) and R66(20) rings (Fig. 5).

Thus, the modes of supramolecular aggregation in (I) and (II) are entirely different from one another. In addition, they differ from that in the related triazole, compound (IV), where only two of the three available N—H bonds participate in the aggregation to form a C(4)C(5)[R22(7)] chain of rings (Boechat et al., 2004). However, compounds (II) and (III) are nearly isostructural, when due account is taken of the space-group settings employed, P21/c for compound (I) [(II)?] reported here and P21/n for (III) reported by Lynch (2001). Both compounds form sheets of alternating R22(8) and R66(20) rings, so that the description of the supramolecular aggregation in (III) as three-dimensional (Lynch, 2001) is, in fact, incorrect.

Experimental top

To a mixture of equimolar quantities (75 mmol of each) of the thiosemicarbazide H2NCSNHNH2 and the appropriate carboxylic acid RCO2H (R = H or CF3), sulfuric acid (49 mmol) was added dropwise at ambient temperature. The reaction mixtures were then heated at 373 K for 7–10 h with stirring, cooled, poured onto ice–water and rendered alkaline with aqueous sodium hydroxide solution. The resulting solid products were collected by filtration, washed with water, dried and recrystallized from ethanol, to yield crystals of compounds (I) and (II) suitable for single-crystal X-ray diffraction. Analysis for (I): 10 h reaction, 74% yield, m.p. 464–465 K; 1H NMR (MeOD, δ, p.p.m.): 7.06 (s, 1H), 8.54 (s, 2H, NH2); 13C NMR (MeOD, δ, p.p.m.): 144.8 (C1), 171.2 (C2); IR (KBr, ν, cm-1): 3286 and 3091 (N—H), 1618 (CN), 1509 (NH2), 1021 (CS). Analysis for (II): 7 h reaction, 85% yield, m.p. 489–491 K; 1H NMR (MeOD, δ, p.p.m.): 7.71 (s, NH2); 13C NMR (MeOD, δ, p.p.m.): 121.1 (q, CF3, J = 269 Hz), 146.8 (q, C2, J = 38 Hz), 173.8 (C1); 19F NMR (MeOD, δ, p.p.m.): -61.45 (CF3); IR (KBr, ν, cm-1): 3303 and 3127 (N—H), 1640 (CN), 1519 (NH2), 1075 (CS), 1193 and 745 (CF3).

Refinement top

The space groups P21/n and P21/c for compounds (I) and (II), respectively, were uniquely assigned from the systematic absences. All H atoms were located in difference maps. The coordinates of the H atom bonded to C in compound (I) were freely refined, giving a C—H distance of 0.95 (3) Å. H atoms bonded to N were allowed to ride at the positions found from the difference maps, with Uiso(H) = 1.2Ueq(N); the resulting N—H distances were in the range 0.84–0.89 Å. In (II), the anisotropic displacement parameters for the F atoms suggest that there may some libration of the CF3 group about the C5—C51 bond.

Structure description top

The structure of 2-amino-1,3,4-thiadiazole, (I), was reported several years ago (Khusenov et al., 1997). The use of room-temperature diffraction data gave a final R of 0.079, but no H-atom coordinates were reported, so that it is not possible fully to analyse the supramolecular aggregation. We have now reinvestigated this compound using diffraction data collected at 120 K, together with the substituted analogue 2-amino-5-trifluoromethyl-1,3,4-thiadiazole, (II), which is itself closely related to both 2-amino-5-methyl-1,3,4-thiadiazole, (III) (Lynch, 2001), and 5-amino-3-trifluoromethyl-1H-1,2,4-triazole, (IV) (Borbulevych et al., 1998; Boechat et al., 2004).

Within the molecules of (I) and (II) (Figs. 1 and 2), the corresponding bond distances (Table 1) are fairly similar, and they show no real evidence for aromatic type π-electron delocalization. In particular, the C—S distances are all much longer than such bonds in thiophenes (Allen et al., 1987). In each of (I) and (II), the C—S—C angle is less than 90°, with compensatory larger angles elsewhere in the rings (Table 1).

In each of (I) and (II), the amino groups act as double donors in N—H···N hydrogen bonds (Tables 2 and 3). However, in (I), the resulting supramolecular structure is one-dimensional, while in (II) it is two-dimensional. In compound (I), the amino atom N2 in the molecule at (x, y, z) acts as hydrogen-bond donor, via atoms H21 and H22, respectively, to atoms N at (1 - x, 1 - y, 1 - z) and atom N4 at (x, y, -1 + z). Propagation by inversion and translation of these two interactions generates a chain of edge-fused rings running parallel to the [001] direction, with R22(8) (Bernstein et al., 1995) rings centred at (1/2, 1/2, n + 1/2) (n = zero or integer) and R44(10) rings centred at (1/2, 1/2, n) (n = zero or integer) (Fig. 3).

The molecules of compound (II) are also linked into centrosymmetric R22(8) dimers (Fig. 4) by paired N—H···N hydrogen bonds (Table 3), exactly the same as those in compound (I). However, the further linking of these dimers generates a (100) sheet, rather than an [001] chain. The amino atoms N2 in the molecules at (x, y, z) and (1 - x, 1 - y, 1 - z), components of the R22(8) dimer centred at (1/2, 1/2, 1/2), act as hydrogen-bond donors, via atom H21, to the ring atoms N4 in the molecules at (x, 1/2 - y, 1/2 + z) and (1 - x, 1/2 + y, 1/2 - z), respectively, which are components of the R22(8) dimers centred at (1/2, 0, 1) and (1/2, 1, 0), respectively. Similarly, atoms N4 in the molecules at (x, y, z) and (1 - x, 1 - y, 1 - z) accept hydrogen bonds from atom N2 in the molecules at (x, 1/2 - y, -1/2 + z) and (1 - x, 1/2 + y, 3/2 - z), respectively, which are themselves components of the dimers centred at (1/2, 0, 0) and (1/2, 1, 1). Propagation of these two hydrogen bonds then generates a (100) sheet in the form of a (6,3) net (Batten & Robson, 1998) built from alternating R22(8) and R66(20) rings (Fig. 5).

Thus, the modes of supramolecular aggregation in (I) and (II) are entirely different from one another. In addition, they differ from that in the related triazole, compound (IV), where only two of the three available N—H bonds participate in the aggregation to form a C(4)C(5)[R22(7)] chain of rings (Boechat et al., 2004). However, compounds (II) and (III) are nearly isostructural, when due account is taken of the space-group settings employed, P21/c for compound (I) [(II)?] reported here and P21/n for (III) reported by Lynch (2001). Both compounds form sheets of alternating R22(8) and R66(20) rings, so that the description of the supramolecular aggregation in (III) as three-dimensional (Lynch, 2001) is, in fact, incorrect.

Computing details top

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: WinGX (Farrugia, 1999) and SIR92 (Altomare et al., 1993); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. The molecule of compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The molecule of compound (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. Part of the crystal structure of compound (I), showing the formation of an [001] chain of edge-fused R22(8) and R44(10) rings. For the sake of clarity, the H atom bonded to atom C5 has been omitted. The atoms marked with an asterisk (*), a hash (#), a dollar sign ($), an ampersand (&) or an `at' sign (@) are at the symmetry positions (1 - x, 1 - y, 1 - z), (x, y, -1 + z), (1 - x, 1 - y, -z), (x, y, 1 + z) and (1 - x, 1 - y, 2 - z), respectively.
[Figure 4] Fig. 4. Part of the crystal structure of compound (II), showing the formation of a centrosymmetric R22(8) dimer. The atoms marked with an asterisk (*) are at the symmetry position (1 - x, 1 - y, 1 - z).
[Figure 5] Fig. 5. A stereoview of part of the crystal structure of compound (II), showing the formation of a (100) sheet of alternating R22(8) and R66(20) rings.
(I) 2-amino-1,3,4-thiadiazole top
Crystal data top
C2H3N3SF(000) = 208
Mr = 101.13Dx = 1.647 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 936 reflections
a = 5.5718 (5) Åθ = 3.0–27.6°
b = 13.4573 (17) ŵ = 0.60 mm1
c = 5.7875 (5) ÅT = 120 K
β = 109.984 (6)°Needle, colourless
V = 407.83 (7) Å30.15 × 0.04 × 0.02 mm
Z = 4
Data collection top
Nonius KappaCCD area-detector
diffractometer
936 independent reflections
Radiation source: Bruker Nonius FR91 rotating anode736 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.096
Detector resolution: 9.091 pixels mm-1θmax = 27.6°, θmin = 3.0°
φ and ω scansh = 77
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1717
Tmin = 0.919, Tmax = 0.988l = 67
6842 measured reflections
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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.102H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.056P)2]
where P = (Fo2 + 2Fc2)/3
936 reflections(Δ/σ)max = 0.001
59 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.38 e Å3
Crystal data top
C2H3N3SV = 407.83 (7) Å3
Mr = 101.13Z = 4
Monoclinic, P21/nMo Kα radiation
a = 5.5718 (5) ŵ = 0.60 mm1
b = 13.4573 (17) ÅT = 120 K
c = 5.7875 (5) Å0.15 × 0.04 × 0.02 mm
β = 109.984 (6)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
936 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
736 reflections with I > 2σ(I)
Tmin = 0.919, Tmax = 0.988Rint = 0.096
6842 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.102H-atom parameters constrained
S = 1.08Δρmax = 0.39 e Å3
936 reflectionsΔρmin = 0.38 e Å3
59 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.09495 (9)0.66383 (5)0.20459 (8)0.0231 (2)
N20.3077 (3)0.55639 (16)0.1828 (3)0.0265 (5)
N30.2533 (3)0.57916 (15)0.5659 (3)0.0207 (4)
N40.0865 (3)0.62459 (16)0.6651 (3)0.0225 (5)
C20.1817 (3)0.59265 (18)0.3254 (3)0.0192 (5)
C50.0989 (4)0.67071 (19)0.5026 (4)0.0231 (5)
H210.43820.51780.24850.032*
H220.24230.57050.02310.032*
H50.229 (4)0.709 (2)0.531 (4)0.033 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0227 (3)0.0278 (4)0.0179 (3)0.0044 (2)0.0057 (2)0.0033 (2)
N20.0253 (8)0.0391 (15)0.0153 (8)0.0089 (8)0.0073 (6)0.0045 (8)
N30.0229 (8)0.0224 (13)0.0171 (7)0.0007 (7)0.0072 (6)0.0006 (7)
N40.0262 (9)0.0229 (13)0.0201 (8)0.0012 (8)0.0099 (7)0.0023 (7)
C20.0204 (9)0.0181 (13)0.0181 (9)0.0012 (8)0.0053 (7)0.0020 (8)
C50.0253 (10)0.0239 (15)0.0219 (10)0.0005 (9)0.0104 (8)0.0006 (9)
Geometric parameters (Å, º) top
S1—C51.735 (2)N2—H220.89
S1—C21.745 (2)N3—N41.390 (2)
C2—N31.323 (2)N4—C51.293 (3)
C2—N21.345 (3)C5—H50.95 (3)
N2—H210.87
C5—S1—C286.59 (10)H21—N2—H22124.5
N3—C2—N2124.25 (19)C2—N3—N4111.73 (16)
N3—C2—S1113.86 (15)C5—N4—N3113.04 (16)
N2—C2—S1121.89 (14)N4—C5—S1114.78 (16)
C2—N2—H21118.9N4—C5—H5127.2 (13)
C2—N2—H22116.4S1—C5—H5118.0 (14)
C5—S1—C2—N30.45 (18)C2—N3—N4—C50.8 (3)
C5—S1—C2—N2180.0 (2)N3—N4—C5—S10.4 (3)
N2—C2—N3—N4179.7 (2)C2—S1—C5—N40.00 (19)
S1—C2—N3—N40.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H21···N3i0.872.132.999 (3)175
N2—H22···N4ii0.892.082.969 (2)172
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y, z1.
(II) 2-amino-5-trifluoromethyl-1,3,4-thiadiazole top
Crystal data top
C3H2F3N3SF(000) = 336
Mr = 169.14Dx = 1.841 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1386 reflections
a = 9.1082 (12) Åθ = 3.6–27.5°
b = 6.9373 (10) ŵ = 0.51 mm1
c = 10.8048 (14) ÅT = 120 K
β = 116.656 (9)°Plate, colourless
V = 610.15 (14) Å30.32 × 0.24 × 0.06 mm
Z = 4
Data collection top
Nonius KappaCCD area-detector
diffractometer
1386 independent reflections
Radiation source: Bruker Nonius FR91 rotating anode1093 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.6°
φ and ω scansh = 1111
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 99
Tmin = 0.853, Tmax = 0.970l = 1413
6231 measured reflections
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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0491P)2 + 0.4024P]
where P = (Fo2 + 2Fc2)/3
1386 reflections(Δ/σ)max < 0.001
91 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.35 e Å3
Crystal data top
C3H2F3N3SV = 610.15 (14) Å3
Mr = 169.14Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.1082 (12) ŵ = 0.51 mm1
b = 6.9373 (10) ÅT = 120 K
c = 10.8048 (14) Å0.32 × 0.24 × 0.06 mm
β = 116.656 (9)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
1386 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1093 reflections with I > 2σ(I)
Tmin = 0.853, Tmax = 0.970Rint = 0.044
6231 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.113H-atom parameters constrained
S = 1.10Δρmax = 0.33 e Å3
1386 reflectionsΔρmin = 0.35 e Å3
91 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.24020 (8)0.10495 (9)0.55838 (6)0.0289 (2)
F10.2190 (2)0.2644 (3)0.2778 (2)0.0675 (6)
F20.0036 (2)0.1325 (2)0.25331 (19)0.0535 (5)
F30.1382 (3)0.2906 (3)0.43495 (19)0.0639 (6)
N20.4169 (3)0.4342 (3)0.6332 (2)0.0331 (5)
N30.3963 (2)0.2678 (3)0.43721 (19)0.0281 (5)
N40.3250 (2)0.1038 (3)0.3623 (2)0.0267 (5)
C20.3625 (3)0.2894 (4)0.5439 (2)0.0258 (5)
C50.2433 (3)0.0068 (4)0.4127 (2)0.0267 (5)
C510.1499 (3)0.1710 (4)0.3435 (3)0.0334 (6)
H210.47150.52350.62210.040*
H220.39110.44000.70120.040*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0330 (4)0.0325 (4)0.0262 (3)0.0023 (3)0.0176 (3)0.0003 (2)
F10.0644 (13)0.0606 (12)0.0989 (16)0.0210 (10)0.0557 (12)0.0473 (12)
F20.0353 (9)0.0412 (10)0.0597 (11)0.0039 (8)0.0003 (9)0.0050 (8)
F30.0956 (16)0.0394 (10)0.0493 (10)0.0199 (10)0.0260 (11)0.0060 (8)
N20.0406 (13)0.0399 (12)0.0261 (10)0.0116 (10)0.0213 (10)0.0075 (9)
N30.0321 (11)0.0327 (11)0.0224 (10)0.0026 (9)0.0148 (9)0.0021 (8)
N40.0277 (11)0.0296 (11)0.0250 (10)0.0016 (9)0.0136 (9)0.0007 (8)
C20.0246 (12)0.0314 (13)0.0238 (11)0.0001 (10)0.0132 (10)0.0027 (9)
C50.0267 (12)0.0284 (12)0.0259 (11)0.0040 (10)0.0126 (10)0.0019 (10)
C510.0356 (14)0.0322 (13)0.0349 (14)0.0019 (11)0.0180 (12)0.0007 (11)
Geometric parameters (Å, º) top
S1—C51.727 (2)N3—N41.378 (3)
S1—C21.749 (2)N4—C51.291 (3)
C2—N21.325 (3)C5—C511.494 (4)
C2—N31.328 (3)C51—F11.312 (3)
N2—H210.84C51—F21.324 (3)
N2—H220.87C51—F31.330 (3)
C5—S1—C286.31 (11)N4—C5—C51121.7 (2)
N2—C2—N3124.1 (2)N4—C5—S1115.29 (19)
N2—C2—S1122.35 (17)C51—C5—S1122.87 (18)
N3—C2—S1113.56 (18)F1—C51—F2107.8 (2)
C2—N2—H21120.7F1—C51—F3108.1 (2)
C2—N2—H22119.8F2—C51—F3105.2 (2)
H21—N2—H22119.4F1—C51—C5112.0 (2)
C2—N3—N4111.81 (19)F2—C51—C5112.2 (2)
C5—N4—N3113.03 (19)F3—C51—C5111.2 (2)
C5—S1—C2—N2179.1 (2)C2—S1—C5—C51176.7 (2)
C5—S1—C2—N30.03 (18)N4—C5—C51—F131.1 (3)
N2—C2—N3—N4179.5 (2)S1—C5—C51—F1152.8 (2)
S1—C2—N3—N40.4 (3)N4—C5—C51—F290.3 (3)
C2—N3—N4—C50.7 (3)S1—C5—C51—F285.8 (3)
N3—N4—C5—C51177.1 (2)N4—C5—C51—F3152.2 (2)
N3—N4—C5—S10.7 (3)S1—C5—C51—F331.7 (3)
C2—S1—C5—N40.45 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H21···N3i0.842.162.985 (3)171
N2—H22···N4ii0.872.102.959 (3)169
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1/2, z+1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC2H3N3SC3H2F3N3S
Mr101.13169.14
Crystal system, space groupMonoclinic, P21/nMonoclinic, P21/c
Temperature (K)120120
a, b, c (Å)5.5718 (5), 13.4573 (17), 5.7875 (5)9.1082 (12), 6.9373 (10), 10.8048 (14)
β (°) 109.984 (6) 116.656 (9)
V3)407.83 (7)610.15 (14)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.600.51
Crystal size (mm)0.15 × 0.04 × 0.020.32 × 0.24 × 0.06
Data collection
DiffractometerNonius KappaCCD area-detectorNonius KappaCCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.919, 0.9880.853, 0.970
No. of measured, independent and
observed [I > 2σ(I)] reflections
6842, 936, 736 6231, 1386, 1093
Rint0.0960.044
(sin θ/λ)max1)0.6530.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.102, 1.08 0.045, 0.113, 1.10
No. of reflections9361386
No. of parameters5991
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.39, 0.380.33, 0.35

Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, WinGX (Farrugia, 1999) and SIR92 (Altomare et al., 1993), OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N2—H21···N3i0.872.132.999 (3)175
N2—H22···N4ii0.892.082.969 (2)172
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y, z1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N2—H21···N3i0.842.162.985 (3)171
N2—H22···N4ii0.872.102.959 (3)169
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1/2, z+1/2.
Selected geometric parameters (Å, °) for compounds (I) and (II) top
Parameter(I)(II)
S1—C21.745 (2)1.749 (2)
C2—N31.323 (2)1.328 (3)
N3—N41.390 (2)1.378 (3)
N4—C51.293 (3)1.291 (3)
C5—S11.735 (2)1.727 (2)
C2—N21.345 (3)1.325 (3)
C5—C511.494 (4)
C5—S1—C286.59 (10)86.31 (11)
S1—C2—N3113.86 (15)113.56 (18)
C2—N3—N4111.73 (16)111.81 (19)
N3—N4—C5113.04 (16)113.03 (19)
N4—C5—S1114.78 (16)115.29 (19)
S1—C2—N2121.89 (14)122.35 (17)
N3—C2—N2124.25 (19)124.1 (2)
 

Acknowledgements

The X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff for all their help and advice. SMSVW thanks CNPq and FAPERJ for financial support.

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CSD CrossRef Web of Science Google Scholar
First citationAltomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350.  CrossRef Web of Science IUCr Journals Google Scholar
First citationBatten, S. R. & Robson, R. (1998). Angew. Chem. Int. Ed. 37, 1460–1494.  Web of Science CrossRef Google Scholar
First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
First citationBoechat, N., Dutra, K. D. B., Valverde, A. L., Wardell, S. M. S. V., Low, J. N. & Glidewell, C. (2004). Acta Cryst. C60, o733–o736.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationBorbulevych, O. Y., Shishkin, O. V., Desenko, S. M., Chernenko, V. N. & Orlov, V. D. (1998). Acta Cryst. C54, 442–444.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
First citationFerguson, G. (1999). PRPKAPPA. University of Guelph, Canada.  Google Scholar
First citationKhusenov, K. S., Umarov, B. B., Ishankhodzhaeva, M. M., Parpiev, N. A., Talipov, S. A. & Ibragimov, B. T. (1997). Russ. J. Coord. Chem. 23, 555–559; Chem. Abstr. 127, 302376x.  Google Scholar
First citationLynch, D. E. (2001). Acta Cryst. C57, 1201–1203.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationMcArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.  Google Scholar
First citationNonius (1999). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.  Google Scholar
First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.  Google Scholar
First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds