organic compounds
1,3-Bis(1-methyl-5-thioxo-1,2,4-triazolin-4-yl)urea
aUniversity of Innsbruck, Faculty of Chemistry and Pharmacy, Innrain 80, 6020 Innsbruck, Austria, and bUniversity of Innsbruck, Institute of Mineralogy and Petrography, Innrain 52, 6020 Innsbruck, Austria
*Correspondence e-mail: gerhard.laus@uibk.ac.at
The title compound, C7H10N8OS2, was obtained by acylation of 4-amino-1-methyl-1,2,4-triazoline-5-thione with triphosgene. The contains two half molecules. The full molecules are generated by twofold rotation axes. In the crystal, the molecules associate through bifurcated (N—H)2⋯O hydrogen bonds into chains extending in the b-axis direction.
Keywords: crystal structure; carbohydrazide; N—H⋯O hydrogen bonds; triazole; urea.
CCDC reference: 1486393
Structure description
The . The amidic NH atoms adopt an anti relationship to the carbonyl group. Each molecule donates two N—H hydrogen bonds to the O atom of the O=C carbonyl group of one neighbouring molecule, forming infinite chains (Fig. 2). The intermolecular linkage is described as R21(6) in graph-set notation (Etter, 1990), denoting a hydrogen-bonded ring motif consisting of six atoms with two donors and one acceptor. The chains extend in opposite directions along the b axis. The hydrogen-bond parameters are summarized in Table 1, and the crystal packing is shown in Fig. 2.
contains two half-molecules. The fragments are completed by twofold rotation axes through the C4=O1 and C8=O2 carbonyl bonds. The molecular structures of the two independent molecules of the title compound are shown in Fig. 1
|
Chains formed by bifurcated N—H⋯O hydrogen bonds are a typical pattern in the crystal structures of symmetrically N,N′-disubstituted ureas (Custelcean, 2008). The more closely related 1,5-bis(benzylidene)carbohydrazides (Kolb et al., 1994; Li et al., 2009; Rubčić et al., 2014) exhibit a similar architecture.
Synthesis and crystallization
A solution of 4-amino-1-methyl-1,2,4-triazoline-5-thione (Laus et al., 2014) (70 mg, 0.54 mmol) and triphosgene (74 mg, 0.25 mmol) in CH2Cl2 (2 ml) was stirred at room temperature overnight. The solvent was removed under reduced pressure, and the residue was dissolved in hot MeOH (1 ml). On cooling to 253 K the product was obtained as colourless crystals (47 mg, 61%), m.p. 497–498 K.
1H NMR (300 MHz, DMSO-d6): δ 3.68 (s, 3H), 8.76 (s, 1H), 11.0 (br s, 2H) p.p.m. 13C NMR (75 MHz, DMSO-d6): δ 36.7 (2 C), 141.7 (2 C), 155.3, 166.2 (2 C) p.p.m. IR: ν 3264, 3223, 3114, 3040, 2940, 1689, 1532, 1461, 1380, 1341, 1238, 1202, 1159, 962, 878, 836, 766, 735, 623 cm−1.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1486393
10.1107/S2414314616009925/lh4009sup1.cif
contains datablocks LA233, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616009925/lh4009Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616009925/lh4009Isup3.mol
Supporting information file. DOI: 10.1107/S2414314616009925/lh4009Isup4.cml
Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell
CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: Mercury (Macrae et al., 2006).C7H10N8OS2 | F(000) = 592 |
Mr = 286.35 | Dx = 1.489 Mg m−3 |
Monoclinic, P2/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yac | Cell parameters from 3315 reflections |
a = 16.5100 (8) Å | θ = 3.2–28.7° |
b = 4.4590 (2) Å | µ = 0.42 mm−1 |
c = 17.5229 (8) Å | T = 173 K |
β = 98.108 (5)° | Fragment, colourless |
V = 1277.11 (10) Å3 | 0.32 × 0.16 × 0.16 mm |
Z = 4 |
Oxford Diffraction Xcalibur Ruby Gemini ultra diffractometer | 2347 independent reflections |
Graphite monochromator | 1999 reflections with I > 2σ(I) |
Detector resolution: 10.3575 pixels mm-1 | Rint = 0.027 |
ω scans | θmax = 25.4°, θmin = 3.2° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | h = −19→19 |
Tmin = 0.906, Tmax = 1 | k = −5→4 |
7200 measured reflections | l = −21→17 |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.078 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0258P)2 + 0.834P] where P = (Fo2 + 2Fc2)/3 |
2347 reflections | (Δ/σ)max < 0.001 |
175 parameters | Δρmax = 0.31 e Å−3 |
2 restraints | Δρmin = −0.29 e Å−3 |
Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44 (release 25-10-2010 CrysAlis171 .NET) (compiled Oct 25 2010,18:11:34) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 | ||
S2 | 0.26495 (3) | −0.61481 (13) | 0.04670 (3) | 0.03468 (16) | |
S1 | −0.03987 (4) | 0.10034 (14) | 0.23836 (3) | 0.03999 (17) | |
N4 | −0.13996 (8) | 0.1301 (3) | 0.34860 (8) | 0.0202 (3) | |
N8 | 0.15021 (8) | −0.5348 (3) | 0.14215 (8) | 0.0201 (3) | |
N2 | −0.07827 (10) | −0.1375 (4) | 0.44368 (9) | 0.0351 (4) | |
N5 | 0.11782 (9) | −0.3325 (4) | 0.03299 (8) | 0.0246 (4) | |
N7 | 0.19327 (10) | −0.6770 (4) | 0.20465 (9) | 0.0240 (4) | |
N3 | −0.20273 (9) | 0.2794 (3) | 0.30443 (9) | 0.0232 (4) | |
O1 | −0.25 | −0.1591 (4) | 0.25 | 0.0347 (5) | |
C3 | −0.06949 (11) | 0.0319 (4) | 0.32286 (10) | 0.0213 (4) | |
O2 | 0.25 | −0.2394 (4) | 0.25 | 0.0346 (5) | |
N6 | 0.05551 (9) | −0.2662 (4) | 0.07491 (9) | 0.0336 (4) | |
N1 | −0.03351 (9) | −0.1290 (4) | 0.38286 (8) | 0.0245 (4) | |
C7 | 0.17800 (10) | −0.4933 (4) | 0.07239 (10) | 0.0201 (4) | |
C6 | 0.07744 (11) | −0.3923 (5) | 0.14090 (11) | 0.0292 (5) | |
H6 | 0.0468 | −0.3861 | 0.1829 | 0.035* | |
C4 | −0.25 | 0.1126 (6) | 0.25 | 0.0220 (6) | |
C2 | −0.14226 (11) | 0.0200 (5) | 0.42055 (11) | 0.0319 (5) | |
H2 | −0.1855 | 0.0549 | 0.4499 | 0.038* | |
C1 | 0.04523 (12) | −0.2800 (5) | 0.38851 (11) | 0.0342 (5) | |
H1A | 0.0463 | −0.4082 | 0.3432 | 0.051* | |
H1B | 0.0535 | −0.4032 | 0.4353 | 0.051* | |
H1C | 0.0889 | −0.1302 | 0.3908 | 0.051* | |
C8 | 0.25 | −0.5107 (6) | 0.25 | 0.0209 (5) | |
C5 | 0.11379 (12) | −0.2272 (5) | −0.04599 (11) | 0.0349 (5) | |
H5A | 0.1586 | −0.0862 | −0.0495 | 0.052* | |
H5B | 0.0613 | −0.1263 | −0.0616 | 0.052* | |
H5C | 0.1187 | −0.3983 | −0.0801 | 0.052* | |
H7 | 0.1984 (11) | −0.861 (3) | 0.2012 (11) | 0.022 (5)* | |
H3 | −0.1963 (11) | 0.464 (4) | 0.2968 (11) | 0.026 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S2 | 0.0233 (3) | 0.0416 (3) | 0.0397 (3) | 0.0065 (2) | 0.0063 (2) | −0.0075 (2) |
S1 | 0.0508 (3) | 0.0496 (4) | 0.0214 (3) | 0.0104 (3) | 0.0119 (2) | 0.0080 (2) |
N4 | 0.0187 (7) | 0.0204 (8) | 0.0198 (7) | 0.0013 (6) | −0.0028 (6) | 0.0040 (6) |
N8 | 0.0218 (8) | 0.0207 (8) | 0.0164 (7) | 0.0031 (6) | −0.0023 (6) | 0.0015 (6) |
N2 | 0.0277 (9) | 0.0534 (12) | 0.0251 (9) | 0.0094 (8) | 0.0065 (7) | 0.0170 (8) |
N5 | 0.0197 (8) | 0.0357 (9) | 0.0184 (8) | 0.0037 (7) | 0.0024 (6) | 0.0054 (7) |
N7 | 0.0334 (9) | 0.0130 (8) | 0.0219 (8) | 0.0007 (7) | −0.0084 (7) | 0.0019 (6) |
N3 | 0.0246 (8) | 0.0122 (8) | 0.0292 (8) | 0.0014 (6) | −0.0091 (7) | 0.0015 (7) |
O1 | 0.0340 (11) | 0.0115 (10) | 0.0524 (13) | 0 | −0.0156 (10) | 0 |
C3 | 0.0236 (9) | 0.0203 (9) | 0.0188 (9) | −0.0019 (7) | −0.0015 (7) | −0.0011 (7) |
O2 | 0.0548 (13) | 0.0124 (10) | 0.0309 (10) | 0 | −0.0138 (9) | 0 |
N6 | 0.0262 (9) | 0.0472 (11) | 0.0288 (9) | 0.0132 (8) | 0.0085 (7) | 0.0122 (8) |
N1 | 0.0215 (8) | 0.0328 (9) | 0.0184 (8) | 0.0049 (7) | 0.0003 (6) | 0.0053 (7) |
C7 | 0.0197 (9) | 0.0205 (9) | 0.0188 (9) | −0.0025 (7) | −0.0022 (7) | −0.0035 (7) |
C6 | 0.0266 (10) | 0.0367 (12) | 0.0252 (10) | 0.0074 (9) | 0.0066 (8) | 0.0050 (9) |
C4 | 0.0211 (13) | 0.0163 (14) | 0.0271 (14) | 0 | −0.0020 (11) | 0 |
C2 | 0.0235 (10) | 0.0465 (13) | 0.0260 (10) | 0.0040 (9) | 0.0048 (8) | 0.0115 (9) |
C1 | 0.0275 (10) | 0.0451 (13) | 0.0285 (10) | 0.0151 (9) | −0.0013 (9) | 0.0010 (9) |
C8 | 0.0294 (14) | 0.0149 (13) | 0.0175 (12) | 0 | 0.0002 (11) | 0 |
C5 | 0.0289 (10) | 0.0543 (14) | 0.0209 (10) | 0.0006 (10) | 0.0018 (8) | 0.0121 (9) |
S2—C7 | 1.6551 (18) | N3—H3 | 0.842 (15) |
S1—C3 | 1.6520 (18) | O1—C4 | 1.211 (3) |
N4—C2 | 1.359 (2) | C3—N1 | 1.340 (2) |
N4—N3 | 1.3749 (19) | O2—C8 | 1.210 (3) |
N4—C3 | 1.377 (2) | N6—C6 | 1.291 (2) |
N8—C6 | 1.357 (2) | N1—C1 | 1.455 (2) |
N8—N7 | 1.3737 (19) | C6—H6 | 0.95 |
N8—C7 | 1.377 (2) | C4—N3i | 1.365 (2) |
N2—C2 | 1.286 (2) | C2—H2 | 0.95 |
N2—N1 | 1.380 (2) | C1—H1A | 0.98 |
N5—C7 | 1.336 (2) | C1—H1B | 0.98 |
N5—N6 | 1.378 (2) | C1—H1C | 0.98 |
N5—C5 | 1.454 (2) | C8—N7ii | 1.360 (2) |
N7—C8 | 1.360 (2) | C5—H5A | 0.98 |
N7—H7 | 0.829 (15) | C5—H5B | 0.98 |
N3—C4 | 1.365 (2) | C5—H5C | 0.98 |
C2—N4—N3 | 125.45 (16) | N8—C7—S2 | 127.42 (13) |
C2—N4—C3 | 108.93 (14) | N6—C6—N8 | 110.76 (17) |
N3—N4—C3 | 125.05 (15) | N6—C6—H6 | 124.6 |
C6—N8—N7 | 125.91 (15) | N8—C6—H6 | 124.6 |
C6—N8—C7 | 109.13 (14) | O1—C4—N3 | 123.04 (11) |
N7—N8—C7 | 124.75 (15) | O1—C4—N3i | 123.04 (11) |
C2—N2—N1 | 104.32 (15) | N3—C4—N3i | 113.9 (2) |
C7—N5—N6 | 113.36 (14) | N2—C2—N4 | 111.14 (17) |
C7—N5—C5 | 126.59 (16) | N2—C2—H2 | 124.4 |
N6—N5—C5 | 120.05 (14) | N4—C2—H2 | 124.4 |
C8—N7—N8 | 116.79 (16) | N1—C1—H1A | 109.5 |
C8—N7—H7 | 120.9 (13) | N1—C1—H1B | 109.5 |
N8—N7—H7 | 116.5 (13) | H1A—C1—H1B | 109.5 |
C4—N3—N4 | 116.15 (15) | N1—C1—H1C | 109.5 |
C4—N3—H3 | 119.6 (13) | H1A—C1—H1C | 109.5 |
N4—N3—H3 | 117.4 (13) | H1B—C1—H1C | 109.5 |
N1—C3—N4 | 102.41 (15) | O2—C8—N7 | 123.05 (11) |
N1—C3—S1 | 130.35 (14) | O2—C8—N7ii | 123.05 (11) |
N4—C3—S1 | 127.25 (13) | N7—C8—N7ii | 113.9 (2) |
C6—N6—N5 | 104.35 (15) | N5—C5—H5A | 109.5 |
C3—N1—N2 | 113.19 (14) | N5—C5—H5B | 109.5 |
C3—N1—C1 | 126.44 (16) | H5A—C5—H5B | 109.5 |
N2—N1—C1 | 120.36 (14) | N5—C5—H5C | 109.5 |
N5—C7—N8 | 102.38 (14) | H5A—C5—H5C | 109.5 |
N5—C7—S2 | 130.21 (14) | H5B—C5—H5C | 109.5 |
C6—N8—N7—C8 | −92.0 (2) | C5—N5—C7—N8 | −178.91 (18) |
C7—N8—N7—C8 | 82.2 (2) | N6—N5—C7—S2 | −178.16 (15) |
C2—N4—N3—C4 | −98.5 (2) | C5—N5—C7—S2 | 1.4 (3) |
C3—N4—N3—C4 | 71.8 (2) | C6—N8—C7—N5 | −1.55 (19) |
C2—N4—C3—N1 | −0.91 (19) | N7—N8—C7—N5 | −176.56 (15) |
N3—N4—C3—N1 | −172.58 (15) | C6—N8—C7—S2 | 178.12 (14) |
C2—N4—C3—S1 | 178.80 (15) | N7—N8—C7—S2 | 3.1 (3) |
N3—N4—C3—S1 | 7.1 (3) | N5—N6—C6—N8 | −0.2 (2) |
C7—N5—N6—C6 | −0.9 (2) | N7—N8—C6—N6 | 176.08 (17) |
C5—N5—N6—C6 | 179.50 (18) | C7—N8—C6—N6 | 1.1 (2) |
N4—C3—N1—N2 | 0.6 (2) | N4—N3—C4—O1 | 15.64 (17) |
S1—C3—N1—N2 | −179.12 (15) | N4—N3—C4—N3i | −164.36 (17) |
N4—C3—N1—C1 | −178.04 (17) | N1—N2—C2—N4 | −0.6 (2) |
S1—C3—N1—C1 | 2.3 (3) | N3—N4—C2—N2 | 172.63 (17) |
C2—N2—N1—C3 | 0.0 (2) | C3—N4—C2—N2 | 1.0 (2) |
C2—N2—N1—C1 | 178.71 (18) | N8—N7—C8—O2 | 19.06 (18) |
N6—N5—C7—N8 | 1.5 (2) | N8—N7—C8—N7ii | −160.94 (18) |
Symmetry codes: (i) −x−1/2, y, −z+1/2; (ii) −x+1/2, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O1iii | 0.84 (2) | 2.02 (2) | 2.753 (2) | 145 (2) |
N7—H7···O2iv | 0.83 (2) | 2.02 (2) | 2.755 (2) | 147 (2) |
Symmetry codes: (iii) x, y+1, z; (iv) x, y−1, z. |
References
Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst. 36, 1103. CrossRef IUCr Journals Google Scholar
Custelcean, R. (2008). Chem. Commun. pp. 295–307. Web of Science CrossRef Google Scholar
Etter, M. C. (1990). Acc. Chem. Res. 23, 120–126. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Kolb, V. M., Robinson, P. D. & Meyers, C. Y. (1994). Acta Cryst. C50, 417–419. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Laus, G., Kahlenberg, V., Wurst, K. & Schottenberger, H. (2014). Z. Naturforsch. Teil B, 69, 950–964. CAS Google Scholar
Li, K., Jiao, J., Wang, Y., Wei, G.-D. & Wang, D. (2009). Acta Cryst. E65, o1846. CSD CrossRef IUCr Journals Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England. Google Scholar
Rubčić, M., Galić, N., Halasz, I., Jednačak, T., Judaš, N., Plavec, J., Šket, P. & Novak, P. (2014). Cryst. Growth Des. 14, 2900–2912. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.