N-Carbethoxy-N'-(3-phenyl-1H-1,2,4-triazol-5-yl)thiourea.

The title compound {systematic name: ethyl N-[N-(3-phenyl-1H-1,2,4-triazol-5-yl)carbamothio-yl]carbamate}, C(12)H(13)N(5)O(2)S, exists in the 3-phenyl-5-thio-ureido-1H-1,2,4-triazole tautomeric form stabilized by intra-molecular hydrogen bonding between the endocyclic NH H atom and the thio-ureido S atom. The mol-ecular structure is also stabilized by intra-molecular N-H⋯O=C hydrogen bonds arranged in an S(6) graph-set motif within the carbethoxy-thio-urea moiety. The mean planes of the phenyl and 1,2,4-triazole rings make a dihedral angle of 7.61 (11)°. In the crystal, the mol-ecules form two types of inversion dimers. Inter-molecular hydrogen bonds are arranged in R(2) (2)(6) and R(2) (2)(8) graph-set motifs, together forming a network parallel to (111).

Related literature

For the synthesis, tautomerism and crystal structure studies of related 1,2,4-triazoles, see: Dolzhenko et al. (2007 ▶, 2009 ▶). For the structures of related carbethoxy­thio­ureas, see: Huang et al. (2009 ▶); Lin et al. (2004 ▶, 2007 ▶); Su et al. (2006 ▶); Zhang et al. (2003 ▶, 2007 ▶). For the graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C12H13N5O2S

M = 291.33

Triclinic,

a = 5.9929 (3) Å

b = 9.4200 (5) Å

c = 12.2000 (7) Å

α = 91.818 (1)°

β = 92.585 (1)°

γ = 101.083 (1)°

V = 674.62 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.25 mm−1

T = 100 K

0.56 × 0.24 × 0.12 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T min = 0.873, T max = 0.971

8943 measured reflections

3092 independent reflections

2828 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.102

S = 1.06

3092 reflections

194 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.59 e Å−3

Δρmin = −0.20 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810002369/gw2076sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810002369/gw2076Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H13N5O2S	Z = 2
Mr = 291.33	F(000) = 304
Triclinic, P1	Dx = 1.434 Mg m−3
Hall symbol: -P 1	Melting point: 454 K
a = 5.9929 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.4200 (5) Å	Cell parameters from 4121 reflections
c = 12.2000 (7) Å	θ = 2.7–27.5°
α = 91.818 (1)°	µ = 0.25 mm−1
β = 92.585 (1)°	T = 100 K
γ = 101.083 (1)°	Rod, colourless
V = 674.62 (6) Å3	0.56 × 0.24 × 0.12 mm

Bruker SMART APEX CCD diffractometer	3092 independent reflections
Radiation source: fine-focus sealed tube	2828 reflections with I > 2σ(I)
graphite	Rint = 0.028
φ and ω scans	θmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −7→7
Tmin = 0.873, Tmax = 0.971	k = −12→12
8943 measured reflections	l = −15→15

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0557P)2 + 0.2404P] where P = (Fo2 + 2Fc2)/3
3092 reflections	(Δ/σ)max = 0.001
194 parameters	Δρmax = 0.59 e Å−3
0 restraints	Δρmin = −0.20 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 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
S1	0.26167 (6)	0.64734 (4)	−0.02591 (3)	0.02072 (12)
O1	0.58945 (18)	0.44334 (11)	0.28112 (8)	0.0204 (2)
O2	0.31338 (18)	0.55681 (11)	0.33852 (8)	0.0217 (2)
N1	−0.1894 (2)	0.78466 (13)	0.22558 (10)	0.0180 (3)
N2	−0.1881 (2)	0.93860 (13)	0.08657 (10)	0.0196 (3)
N3	−0.0355 (2)	0.84999 (13)	0.07092 (10)	0.0190 (3)
H3N	0.052 (3)	0.866 (2)	0.0191 (17)	0.033 (5)*
N4	0.1037 (2)	0.66518 (13)	0.17503 (10)	0.0179 (3)
H4N	0.111 (3)	0.643 (2)	0.2411 (17)	0.028 (5)*
N5	0.3803 (2)	0.52952 (13)	0.15529 (10)	0.0187 (3)
H5N	0.458 (3)	0.494 (2)	0.1140 (15)	0.020 (4)*
C1	−0.5206 (3)	0.91936 (16)	0.33573 (12)	0.0208 (3)
H1	−0.4508	0.8519	0.3742	0.025*
C2	−0.6883 (3)	0.97955 (17)	0.38396 (13)	0.0246 (3)
H2	−0.7334	0.9528	0.4553	0.030*
C3	−0.7902 (3)	1.07873 (17)	0.32819 (14)	0.0254 (3)
H3	−0.9047	1.1199	0.3614	0.030*
C4	−0.7245 (3)	1.11747 (16)	0.22403 (13)	0.0237 (3)
H4	−0.7936	1.1857	0.1861	0.028*
C5	−0.5586 (3)	1.05716 (16)	0.17507 (12)	0.0204 (3)
H5	−0.5154	1.0833	0.1034	0.024*
C6	−0.4547 (2)	0.95789 (15)	0.23090 (12)	0.0175 (3)
C7	−0.2773 (2)	0.89424 (15)	0.17999 (12)	0.0172 (3)
C8	−0.0381 (2)	0.76241 (15)	0.15491 (11)	0.0173 (3)
C9	0.2436 (2)	0.61501 (15)	0.10695 (11)	0.0170 (3)
C10	0.4197 (2)	0.51397 (15)	0.26620 (12)	0.0181 (3)
C11	0.6496 (3)	0.42025 (17)	0.39532 (12)	0.0246 (3)
H11A	0.5123	0.3763	0.4334	0.030*
H11B	0.7187	0.5134	0.4339	0.030*
C12	0.8169 (3)	0.32036 (17)	0.39450 (14)	0.0250 (3)
H12A	0.7455	0.2281	0.3572	0.037*
H12B	0.8636	0.3033	0.4702	0.037*
H12C	0.9508	0.3645	0.3556	0.037*

	U11	U22	U33	U12	U13	U23
S1	0.0269 (2)	0.0220 (2)	0.01582 (19)	0.01013 (15)	0.00368 (14)	0.00310 (13)
O1	0.0255 (5)	0.0203 (5)	0.0183 (5)	0.0113 (4)	0.0017 (4)	0.0021 (4)
O2	0.0270 (6)	0.0238 (5)	0.0175 (5)	0.0120 (4)	0.0040 (4)	0.0029 (4)
N1	0.0203 (6)	0.0153 (6)	0.0188 (6)	0.0047 (5)	0.0010 (5)	0.0011 (5)
N2	0.0205 (6)	0.0206 (6)	0.0194 (6)	0.0083 (5)	0.0000 (5)	0.0019 (5)
N3	0.0212 (6)	0.0206 (6)	0.0174 (6)	0.0088 (5)	0.0035 (5)	0.0041 (5)
N4	0.0225 (6)	0.0187 (6)	0.0141 (6)	0.0078 (5)	0.0020 (5)	0.0025 (5)
N5	0.0220 (6)	0.0190 (6)	0.0174 (6)	0.0093 (5)	0.0039 (5)	0.0006 (5)
C1	0.0230 (7)	0.0193 (7)	0.0214 (7)	0.0074 (6)	−0.0003 (6)	0.0013 (5)
C2	0.0262 (8)	0.0251 (8)	0.0235 (8)	0.0068 (6)	0.0054 (6)	0.0001 (6)
C3	0.0224 (7)	0.0236 (8)	0.0317 (8)	0.0089 (6)	0.0014 (6)	−0.0037 (6)
C4	0.0220 (7)	0.0191 (7)	0.0313 (8)	0.0081 (6)	−0.0035 (6)	0.0004 (6)
C5	0.0214 (7)	0.0183 (7)	0.0211 (7)	0.0032 (5)	−0.0020 (5)	0.0024 (5)
C6	0.0168 (6)	0.0155 (7)	0.0201 (7)	0.0034 (5)	−0.0012 (5)	−0.0016 (5)
C7	0.0172 (7)	0.0159 (6)	0.0185 (7)	0.0039 (5)	−0.0032 (5)	0.0002 (5)
C8	0.0194 (7)	0.0153 (6)	0.0171 (7)	0.0036 (5)	0.0000 (5)	−0.0004 (5)
C9	0.0186 (7)	0.0136 (6)	0.0184 (7)	0.0026 (5)	0.0005 (5)	0.0005 (5)
C10	0.0213 (7)	0.0135 (6)	0.0199 (7)	0.0042 (5)	0.0015 (5)	0.0023 (5)
C11	0.0318 (8)	0.0256 (8)	0.0194 (7)	0.0135 (6)	−0.0016 (6)	0.0021 (6)
C12	0.0249 (8)	0.0235 (8)	0.0285 (8)	0.0094 (6)	−0.0008 (6)	0.0042 (6)

S1—C9	1.6632 (14)	C1—C6	1.394 (2)
O1—C10	1.3274 (17)	C1—H1	0.9500
O1—C11	1.4568 (17)	C2—C3	1.390 (2)
O2—C10	1.2142 (18)	C2—H2	0.9500
N1—C8	1.3194 (18)	C3—C4	1.386 (2)
N1—C7	1.3680 (18)	C3—H3	0.9500
N2—C7	1.3260 (19)	C4—C5	1.385 (2)
N2—N3	1.3674 (17)	C4—H4	0.9500
N3—C8	1.3345 (18)	C5—C6	1.397 (2)
N3—H3N	0.84 (2)	C5—H5	0.9500
N4—C9	1.3440 (18)	C6—C7	1.4685 (19)
N4—C8	1.3845 (18)	C11—C12	1.501 (2)
N4—H4N	0.84 (2)	C11—H11A	0.9900
N5—C10	1.3803 (18)	C11—H11B	0.9900
N5—C9	1.3811 (18)	C12—H12A	0.9800
N5—H5N	0.81 (2)	C12—H12B	0.9800
C1—C2	1.389 (2)	C12—H12C	0.9800
C10—O1—C11	115.00 (11)	C1—C6—C5	119.48 (13)
C8—N1—C7	102.43 (12)	C1—C6—C7	120.00 (13)
C7—N2—N3	102.54 (11)	C5—C6—C7	120.52 (13)
C8—N3—N2	109.22 (12)	N2—C7—N1	114.46 (13)
C8—N3—H3N	131.7 (14)	N2—C7—C6	122.90 (13)
N2—N3—H3N	118.4 (14)	N1—C7—C6	122.64 (13)
C9—N4—C8	128.91 (13)	N1—C8—N3	111.32 (12)
C9—N4—H4N	117.6 (13)	N1—C8—N4	121.13 (13)
C8—N4—H4N	113.1 (13)	N3—C8—N4	127.42 (13)
C10—N5—C9	127.10 (13)	N4—C9—N5	114.77 (12)
C10—N5—H5N	116.8 (13)	N4—C9—S1	125.65 (11)
C9—N5—H5N	115.5 (13)	N5—C9—S1	119.58 (11)
C2—C1—C6	120.04 (14)	O2—C10—O1	125.48 (13)
C2—C1—H1	120.0	O2—C10—N5	125.13 (13)
C6—C1—H1	120.0	O1—C10—N5	109.38 (12)
C1—C2—C3	120.18 (14)	O1—C11—C12	106.95 (12)
C1—C2—H2	119.9	O1—C11—H11A	110.3
C3—C2—H2	119.9	C12—C11—H11A	110.3
C4—C3—C2	119.88 (14)	O1—C11—H11B	110.3
C4—C3—H3	120.1	C12—C11—H11B	110.3
C2—C3—H3	120.1	H11A—C11—H11B	108.6
C5—C4—C3	120.28 (14)	C11—C12—H12A	109.5
C5—C4—H4	119.9	C11—C12—H12B	109.5
C3—C4—H4	119.9	H12A—C12—H12B	109.5
C4—C5—C6	120.13 (14)	C11—C12—H12C	109.5
C4—C5—H5	119.9	H12A—C12—H12C	109.5
C6—C5—H5	119.9	H12B—C12—H12C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5N···S1i	0.81 (2)	2.58 (2)	3.3739 (13)	166.0 (17)
N4—H4N···O2	0.84 (2)	1.97 (2)	2.6448 (16)	137.3 (18)
N3—H3N···S1	0.84 (2)	2.67 (2)	3.0926 (13)	113.0 (16)
N3—H3N···N2ii	0.84 (2)	2.32 (2)	2.9838 (18)	136.5 (18)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5N⋯S1i	0.81 (2)	2.58 (2)	3.3739 (13)	166.0 (17)
N4—H4N⋯O2	0.84 (2)	1.97 (2)	2.6448 (16)	137.3 (18)
N3—H3N⋯S1	0.84 (2)	2.67 (2)	3.0926 (13)	113.0 (16)
N3—H3N⋯N2ii	0.84 (2)	2.32 (2)	2.9838 (18)	136.5 (18)

Symmetry codes: (i) ; (ii) .