Methyl 3-[3-(ethoxy-carbon-yl)thio-ureido]-1H-pyrazole-5-carboxyl-ate.

The title compound, C(9)H(12)N(4)O(4)S, was proven to be the product of the reaction of methyl 5-amino-1H-pyrazole-3-carboxyl-ate with ethyl isothio-cyanato-carbonate. All non-H atoms of the mol-ecule are planar, the mean deviation from the least squares plane being 0.048 Å. The intra-molecular N-H⋯O bond involving the NH-group, which links the thio-urea and pyrazole fragments, closes a six-membered pseudo-heterocyclic ring, and two more hydrogen bonds (N-H⋯O with the participation of the pyrazole NH group and N-H⋯S involving the second thio-urea NH group) link the mol-ecules into infinite chains running along [10].

Related literature

For the structures of similar N-pyrazole-substituted thio­urea derivatives, see: Pask et al. (2006 ▶); Wen et al. (2006 ▶).

Experimental

Crystal data

C9H12N4O4S

M = 272.29

Triclinic,

a = 8.0855 (8) Å

b = 9.0035 (8) Å

c = 9.5959 (9) Å

α = 64.510 (1)°

β = 82.294 (1)°

γ = 78.716 (1)°

V = 617.39 (10) Å3

Z = 2

Mo Kα radiation

μ = 0.28 mm−1

T = 208 K

0.20 × 0.15 × 0.10 mm

Data collection

Siemens P4 diffractometer with APEX CCD detector

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.947, T max = 0.973

5852 measured reflections

2653 independent reflections

2255 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.113

S = 1.04

2653 reflections

166 parameters

H-atom parameters constrained

Δρmax = 0.39 e Å−3

Δρmin = −0.28 e Å−3

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-32 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809016742/dn2451sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809016742/dn2451Isup2.hkl

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

C9H12N4O4S	Z = 2
Mr = 272.29	F(000) = 284
Triclinic, P1	Dx = 1.465 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0855 (8) Å	Cell parameters from 3767 reflections
b = 9.0035 (8) Å	θ = 2.5–27.8°
c = 9.5959 (9) Å	µ = 0.28 mm−1
α = 64.510 (1)°	T = 208 K
β = 82.294 (1)°	Block, colorless
γ = 78.716 (1)°	0.20 × 0.15 × 0.10 mm
V = 617.39 (10) Å3

Siemens P4 diffractometer with APEX CCD	2653 independent reflections
Radiation source: fine-focus sealed tube	2255 reflections with I > 2σ(I)
graphite	Rint = 0.044
φ and ω scans	θmax = 28.2°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −5→10
Tmin = 0.947, Tmax = 0.973	k = −11→11
5852 measured reflections	l = −11→12

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040	H-atom parameters constrained
wR(F2) = 0.113	w = 1/[σ2(Fo2) + (0.0521P)2 + 0.1805P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
2653 reflections	Δρmax = 0.39 e Å−3
166 parameters	Δρmin = −0.28 e Å−3
0 restraints	Extinction correction: SHELXL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.064 (8)

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 > σ(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
C1	0.7861 (3)	0.9454 (2)	−0.0198 (2)	0.0539 (6)
H1A	0.6653	0.9725	−0.0320	0.081*
H1B	0.8446	1.0106	−0.1156	0.081*
H1C	0.8125	0.9706	0.0626	0.081*
C2	0.8414 (3)	0.7653 (2)	0.0194 (2)	0.0451 (5)
H2A	0.8135	0.7375	−0.0619	0.054*
H2B	0.9638	0.7366	0.0301	0.054*
C3	0.7832 (2)	0.5090 (2)	0.22047 (19)	0.0319 (4)
C4	0.6784 (2)	0.27556 (19)	0.44802 (18)	0.0285 (4)
C5	0.7965 (2)	−0.00499 (19)	0.46055 (19)	0.0300 (4)
C6	0.7316 (2)	−0.1229 (2)	0.5968 (2)	0.0310 (4)
H6	0.6562	−0.1048	0.6734	0.037*
C7	0.8050 (2)	−0.2725 (2)	0.59165 (19)	0.0312 (4)
C8	0.7909 (2)	−0.4462 (2)	0.6958 (2)	0.0328 (4)
C9	0.6497 (3)	−0.6292 (2)	0.9141 (2)	0.0435 (5)
H9A	0.6341	−0.6894	0.8550	0.065*
H9B	0.5509	−0.6267	0.9831	0.065*
H9C	0.7486	−0.6844	0.9741	0.065*
N1	0.69023 (19)	0.44206 (16)	0.35749 (16)	0.0322 (3)
H1	0.6316	0.5127	0.3917	0.039*
N2	0.77543 (19)	0.16936 (16)	0.39615 (16)	0.0327 (3)
H2	0.8340	0.2152	0.3099	0.039*
N3	0.9003 (2)	−0.07384 (17)	0.37579 (17)	0.0360 (4)
N4	0.9033 (2)	−0.23814 (17)	0.46052 (17)	0.0344 (3)
H4	0.9626	−0.3141	0.4333	0.041*
O1	0.75193 (17)	0.67399 (14)	0.16595 (14)	0.0374 (3)
O2	0.87813 (18)	0.43041 (15)	0.15826 (15)	0.0425 (3)
O3	0.87755 (18)	−0.56425 (14)	0.67884 (15)	0.0407 (3)
O4	0.67259 (17)	−0.46002 (15)	0.80911 (15)	0.0397 (3)
S1	0.54880 (6)	0.22717 (5)	0.60563 (5)	0.03395 (17)

	U11	U22	U33	U12	U13	U23
C1	0.0681 (15)	0.0334 (10)	0.0449 (11)	−0.0077 (10)	0.0106 (10)	−0.0060 (8)
C2	0.0512 (12)	0.0338 (9)	0.0352 (9)	−0.0029 (8)	0.0133 (8)	−0.0061 (8)
C3	0.0347 (9)	0.0267 (8)	0.0311 (8)	0.0000 (7)	0.0010 (7)	−0.0119 (6)
C4	0.0312 (9)	0.0247 (7)	0.0300 (8)	0.0008 (6)	−0.0025 (7)	−0.0137 (6)
C5	0.0340 (9)	0.0240 (8)	0.0333 (8)	0.0005 (6)	−0.0013 (7)	−0.0154 (7)
C6	0.0343 (9)	0.0257 (8)	0.0346 (8)	0.0005 (6)	0.0007 (7)	−0.0171 (7)
C7	0.0346 (9)	0.0259 (8)	0.0359 (9)	−0.0010 (7)	−0.0003 (7)	−0.0174 (7)
C8	0.0356 (9)	0.0295 (8)	0.0373 (9)	−0.0036 (7)	0.0003 (7)	−0.0189 (7)
C9	0.0499 (12)	0.0310 (9)	0.0460 (11)	−0.0095 (8)	0.0089 (9)	−0.0147 (8)
N1	0.0393 (8)	0.0234 (7)	0.0306 (7)	−0.0001 (6)	0.0074 (6)	−0.0127 (6)
N2	0.0405 (8)	0.0234 (7)	0.0313 (7)	−0.0012 (6)	0.0061 (6)	−0.0124 (6)
N3	0.0436 (9)	0.0251 (7)	0.0383 (8)	−0.0008 (6)	0.0038 (7)	−0.0160 (6)
N4	0.0403 (9)	0.0256 (7)	0.0396 (8)	−0.0003 (6)	0.0042 (7)	−0.0195 (6)
O1	0.0432 (7)	0.0254 (6)	0.0341 (6)	−0.0013 (5)	0.0113 (5)	−0.0091 (5)
O2	0.0514 (8)	0.0321 (7)	0.0377 (7)	0.0001 (6)	0.0138 (6)	−0.0160 (6)
O3	0.0490 (8)	0.0263 (6)	0.0472 (7)	−0.0015 (6)	0.0073 (6)	−0.0204 (6)
O4	0.0455 (8)	0.0274 (6)	0.0448 (7)	−0.0050 (5)	0.0098 (6)	−0.0174 (5)
S1	0.0400 (3)	0.0257 (2)	0.0328 (2)	−0.00173 (17)	0.00760 (18)	−0.01324 (18)

C1—C2	1.486 (3)	C5—N2	1.401 (2)
C1—H1A	0.9700	C6—C7	1.380 (2)
C1—H1B	0.9700	C6—H6	0.9400
C1—H1C	0.9700	C7—N4	1.343 (2)
C2—O1	1.463 (2)	C7—C8	1.466 (2)
C2—H2A	0.9800	C8—O3	1.214 (2)
C2—H2B	0.9800	C8—O4	1.329 (2)
C3—O2	1.214 (2)	C9—O4	1.452 (2)
C3—O1	1.3278 (19)	C9—H9A	0.9700
C3—N1	1.374 (2)	C9—H9B	0.9700
C4—N2	1.338 (2)	C9—H9C	0.9700
C4—N1	1.387 (2)	N1—H1	0.8700
C4—S1	1.6617 (16)	N2—H2	0.8700
C5—N3	1.340 (2)	N3—N4	1.344 (2)
C5—C6	1.397 (2)	N4—H4	0.8700
C2—C1—H1A	109.5	N4—C7—C6	107.60 (14)
C2—C1—H1B	109.5	N4—C7—C8	119.72 (14)
H1A—C1—H1B	109.5	C6—C7—C8	132.67 (16)
C2—C1—H1C	109.5	O3—C8—O4	123.84 (16)
H1A—C1—H1C	109.5	O3—C8—C7	123.32 (16)
H1B—C1—H1C	109.5	O4—C8—C7	112.84 (14)
O1—C2—C1	106.83 (15)	O4—C9—H9A	109.5
O1—C2—H2A	110.4	O4—C9—H9B	109.5
C1—C2—H2A	110.4	H9A—C9—H9B	109.5
O1—C2—H2B	110.4	O4—C9—H9C	109.5
C1—C2—H2B	110.4	H9A—C9—H9C	109.5
H2A—C2—H2B	108.6	H9B—C9—H9C	109.5
O2—C3—O1	125.25 (16)	C3—N1—C4	127.95 (13)
O2—C3—N1	125.62 (15)	C3—N1—H1	116.0
O1—C3—N1	109.13 (13)	C4—N1—H1	116.0
N2—C4—N1	114.69 (14)	C4—N2—C5	129.41 (14)
N2—C4—S1	126.73 (12)	C4—N2—H2	115.3
N1—C4—S1	118.59 (11)	C5—N2—H2	115.3
N3—C5—C6	112.89 (14)	C5—N3—N4	103.49 (14)
N3—C5—N2	114.22 (15)	C7—N4—N3	112.76 (13)
C6—C5—N2	132.89 (15)	C7—N4—H4	123.6
C7—C6—C5	103.26 (14)	N3—N4—H4	123.6
C7—C6—H6	128.4	C3—O1—C2	116.14 (14)
C5—C6—H6	128.4	C8—O4—C9	115.46 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1i	0.87	2.51	3.347 (1)	161
N2—H2···O2	0.87	1.92	2.657 (2)	141
N4—H4···O3ii	0.87	2.03	2.876 (2)	164

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1i	0.87	2.51	3.347 (1)	161
N2—H2⋯O2	0.87	1.92	2.657 (2)	141
N4—H4⋯O3ii	0.87	2.03	2.876 (2)	164

Symmetry codes: (i) ; (ii) .