1,3-Bis(1-methyl-5-thioxo-1,2,4-triazolin-4-yl)urea

Laus, G.; Kahlenberg, V.; Schottenberger, H.

doi:10.1107/S2414314616009925

organic compounds

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ISSN: 2414-3146

Volume 1| Part 6| June 2016| x160992

doi:10.1107/S2414314616009925

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1,3-Bis(1-methyl-5-thioxo-1,2,4-triazolin-4-yl)urea

Gerhard Laus,^a ^* Volker Kahlenberg ^b and Herwig Schottenberger ^a

^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

Edited by A. J. Lough, University of Toronto, Canada (Received 2 June 2016; accepted 17 June 2016; online 24 June 2016)

The title compound, C₇H₁₀N₈OS₂, was obtained by acylation of 4-amino-1-methyl-1,2,4-triazoline-5-thione with triphosgene. The asymmetric unit 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 asymmetric unit 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. 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.

Table 1
Hydrogen-bond geometry (Å, °)

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⋯O2^iv	0.83 (2)	2.02 (2)	2.755 (2)	147 (2)
Symmetry codes: (iii) x, y+1, z; (iv) x, y-1, z.

Figure 1
The two independent molecules of the title compound, showing the atom labels and 50% probability displacement ellipsoids for non-H atoms. [Symmetry codes: (i) − $[{1\over 2}]$ − x, y, $[{1\over 2}]$ − z; (ii) $[{1\over 2}]$ − x, y, $[{1\over 2}]$ − z.]

Figure 2
The crystal packing of the title compound, viewed along the c axis, showing the N—H⋯O hydrogen bonds as dashed lines (see Table 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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₇H₁₀N₈OS₂
M_r	286.35
Crystal system, space group	Monoclinic, P2/n
Temperature (K)	173
a, b, c (Å)	16.5100 (8), 4.4590 (2), 17.5229 (8)
β (°)	98.108 (5)
V (Å³)	1277.11 (10)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.42
Crystal size (mm)	0.32 × 0.16 × 0.16

Data collection
Diffractometer	Oxford Diffraction Xcalibur Ruby Gemini ultra
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ )
T_min, T_max	0.906, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	7200, 2347, 1999
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.078, 1.04
No. of reflections	2347
No. of parameters	175
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.29
Computer programs: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ), SIR2002 (Burla et al., 2003 ), SHELXL97 (Sheldrick, 2008 ), ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2006 ).

Structural data

CCDC reference: 1486393

Crystal structure: contains datablocks LA233, I. DOI: 10.1107/S2414314616009925/lh4009sup1.cif

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

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: 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).

1,3-Bis(1-methyl-5-thioxo-1,2,4-triazolin-4-yl)urea top

Crystal data top

C₇H₁₀N₈OS₂	F(000) = 592
M_r = 286.35	D_x = 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

Data collection top

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	R_int = 0.027
ω scans	θ_max = 25.4°, θ_min = 3.2°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	h = −19→19
T_min = 0.906, T_max = 1	k = −5→4
7200 measured reflections	l = −21→17

Refinement top

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(F_o²) + (0.0258P)² + 0.834P] where P = (F_o² + 2F_c²)/3
2347 reflections	(Δ/σ)_max < 0.001
175 parameters	Δρ_max = 0.31 e Å⁻³
2 restraints	Δρ_min = −0.29 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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···O2^iv	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
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Li, K., Jiao, J., Wang, Y., Wei, G.-D. & Wang, D. (2009). Acta Cryst. E65, o1846. CSD CrossRef IUCr Journals Google Scholar
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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
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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

1,3-Bis(1-methyl-5-thioxo-1,2,4-triazolin-4-yl)urea

Structure description

Synthesis and crystallization

Refinement

Structural data

References

organic compounds