Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
In the crystal structure of the title compound, C8H12N2O2S, the mol­ecules are linked into centrosymmetric dimers by a pair of strong O—H...O hydrogen bonds. Inter­molecular S...S contacts between adjacent dimers generate a sheet-like structure running parallel to the (211) plane.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805038298/rz6140sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805038298/rz6140Isup2.hkl
Contains datablock I

CCDC reference: 296638

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.005 Å
  • Disorder in main residue
  • R factor = 0.054
  • wR factor = 0.152
  • Data-to-parameter ratio = 12.4

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for N1 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C7 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C7' PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.18 PLAT301_ALERT_3_C Main Residue Disorder ......................... 13.00 Perc. PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 5 PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 5
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 10 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Pyrazole and its derivatives represent one of the most important classes of compounds, possessing a wide spectrum of biological activities (Iovu et al., 2003), such as antibacterial, fungicidal, herbicidal and insecticidal. In the course of our systematic studies aimed at the synthesis of new bioactive compounds, we synthesized the title compound, (I), the structure of which is reported here.

The pyrazole ring is planar, the largest deviation from planarity being 0.009 (4) Å for atom C1. Bond distances and angles (Table 1) are as expected for this type of compound. In the crystal structure, centrosymmetrically related molecules are linked into dimers by intermolecular O—H···O hydrogen bonds (Table 2 and Fig. 2), thus generating rings of graph-set motifs R22(8) (Bernstein et al., 1995). Intermolecular contacts between S atoms of adjacent dimers [S1···S1ii = 3.5374 (17) Å; symmetry code: (ii) 1 − x, −y, −z] are observed, generating a sheet-like structure running parallel to the (211) plane.

Experimental top

To a solution of ketene S,S-acetal (23.43 g, 0.1 mol) in ethanol (50 ml), 80% hydrazine hydrate (6.3 g,0.1 mol) was added slowly. The mixture was stirred for 3 h at room temperature to give ethyl 3-methyl-5-methylthio-1H-pyrazol-4-carboxylate, (1). NaOH (1 g) and and Et2SO4 (0.77 g, 5 mmol) in chloroform (50 ml) were added slowly to the mixture of (1) (1.0 g, 5 mmol) with stirring for 5 h at room temperature to give ethyl 1-ethyl-5-methyl-3- methylthiopyrazole-4-carboxylate, (2). Compound (2) was hydrolyzed under reflux for 3 h and after cooling acidified to pH 3.0, to give (I). Single crystals suitable for X-ray diffraction studies were isolated by recrystallization from ethanol and MeCN (m.p. 466.5 K).

Refinement top

All H atoms were placed in calculated positions, with C—H = 0.96 or 0.97 Å and O—H = 0.82 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) values of 1.2 or 1.5 times Ueq of the parent atoms. The ethyl group is disordered; atoms C7 and C8 and related H atoms were refined over two positions with occupancies 0.751 (10) and 0.249 (10) for the major and minor components, respectively.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. View of the title compound, with 35% probability displacement ellipsoids. Only the major component of the disordered C7/C8 ethyl group is shown.
[Figure 2] Fig. 2. Molecular packing of the title compound, viewed along the a axis. Hydrogen bonds and S···S contacts are shown as dashed lines.
1-ethyl-5-methyl-3-methylthio-1H-pyrazole-4-carboxylic acid top
Crystal data top
C8H12N2O2SZ = 2
Mr = 200.27F(000) = 212
Triclinic, P1Dx = 1.321 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.949 (2) ÅCell parameters from 1010 reflections
b = 8.330 (2) Åθ = 2.6–25.0°
c = 8.368 (2) ŵ = 0.29 mm1
α = 71.267 (4)°T = 293 K
β = 80.761 (5)°Prism, colourless
γ = 74.291 (5)°0.22 × 0.18 × 0.12 mm
V = 503.5 (2) Å3
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
1765 independent reflections
Radiation source: fine-focus sealed tube1253 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ϕ and ω scansθmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 97
Tmin = 0.939, Tmax = 0.966k = 97
2645 measured reflectionsl = 99
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)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.152H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0597P)2 + 0.4305P]
where P = (Fo2 + 2Fc2)/3
1765 reflections(Δ/σ)max = 0.002
142 parametersΔρmax = 0.35 e Å3
6 restraintsΔρmin = 0.42 e Å3
Crystal data top
C8H12N2O2Sγ = 74.291 (5)°
Mr = 200.27V = 503.5 (2) Å3
Triclinic, P1Z = 2
a = 7.949 (2) ÅMo Kα radiation
b = 8.330 (2) ŵ = 0.29 mm1
c = 8.368 (2) ÅT = 293 K
α = 71.267 (4)°0.22 × 0.18 × 0.12 mm
β = 80.761 (5)°
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
1765 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1253 reflections with I > 2σ(I)
Tmin = 0.939, Tmax = 0.966Rint = 0.022
2645 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0546 restraints
wR(F2) = 0.152H-atom parameters constrained
S = 1.04Δρmax = 0.35 e Å3
1765 reflectionsΔρmin = 0.42 e Å3
142 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
S10.39085 (14)0.07713 (14)0.17200 (11)0.0691 (4)
O10.4592 (3)0.2942 (3)0.3703 (3)0.0693 (7)
O20.3836 (4)0.3938 (3)0.6462 (3)0.0707 (7)
H20.43840.48590.62850.106*
N10.1322 (5)0.1300 (4)0.5849 (4)0.0924 (12)
N20.1926 (5)0.1983 (4)0.4200 (4)0.0859 (11)
C10.1917 (5)0.0417 (5)0.6442 (4)0.0670 (10)
C20.1440 (6)0.1434 (6)0.8214 (5)0.0830 (13)
H2A0.20950.12560.89860.124*
H2B0.17100.26510.82960.124*
H2C0.02080.10450.84950.124*
C30.2943 (4)0.0945 (4)0.5110 (4)0.0526 (8)
C40.3836 (4)0.2687 (5)0.5080 (4)0.0539 (8)
C50.2901 (5)0.0609 (5)0.3759 (4)0.0584 (9)
C60.3458 (7)0.3092 (6)0.0833 (5)0.0898 (14)
H6A0.22140.35550.08190.135*
H6B0.39950.33790.03030.135*
H6C0.39240.35850.15060.135*
C70.0091 (8)0.2523 (8)0.6644 (7)0.0690 (19)0.751 (10)
H7A0.07190.34900.57840.083*0.751 (10)
H7B0.09210.19100.74060.083*0.751 (10)
C80.0935 (8)0.3146 (9)0.7594 (8)0.083 (2)0.751 (10)
H8A0.15920.21620.83940.125*0.751 (10)
H8B0.01410.39010.81830.125*0.751 (10)
H8C0.17240.37720.68100.125*0.751 (10)
C7'0.108 (2)0.2462 (18)0.6982 (17)0.067 (6)0.249 (10)
H7'10.17150.33760.64820.080*0.249 (10)
H7'20.14890.17910.80890.080*0.249 (10)
C8'0.089 (2)0.323 (2)0.711 (3)0.098 (8)0.249 (10)
H8'10.13000.36690.59930.146*0.249 (10)
H8'20.11410.41560.76140.146*0.249 (10)
H8'30.14720.23330.77890.146*0.249 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0827 (7)0.0813 (7)0.0406 (5)0.0260 (5)0.0116 (4)0.0163 (4)
O10.0772 (17)0.0727 (17)0.0493 (13)0.0098 (13)0.0104 (12)0.0198 (12)
O20.090 (2)0.0600 (16)0.0522 (14)0.0139 (14)0.0078 (13)0.0123 (12)
N10.141 (3)0.062 (2)0.0533 (18)0.013 (2)0.034 (2)0.0176 (16)
N20.128 (3)0.066 (2)0.0478 (17)0.021 (2)0.0248 (18)0.0118 (15)
C10.086 (3)0.060 (2)0.0479 (19)0.0190 (19)0.0153 (18)0.0150 (17)
C20.105 (3)0.077 (3)0.052 (2)0.023 (2)0.028 (2)0.0136 (19)
C30.0540 (19)0.061 (2)0.0433 (17)0.0171 (16)0.0046 (14)0.0171 (15)
C40.0515 (19)0.066 (2)0.0445 (18)0.0175 (17)0.0005 (15)0.0150 (16)
C50.071 (2)0.064 (2)0.0411 (17)0.0213 (18)0.0069 (15)0.0168 (16)
C60.130 (4)0.090 (3)0.049 (2)0.047 (3)0.003 (2)0.006 (2)
C70.066 (4)0.083 (5)0.060 (3)0.023 (3)0.004 (3)0.019 (3)
C80.085 (4)0.093 (5)0.080 (4)0.030 (4)0.006 (3)0.030 (3)
C7'0.128 (17)0.050 (9)0.033 (8)0.028 (10)0.003 (9)0.026 (6)
C8'0.100 (17)0.090 (15)0.086 (14)0.003 (12)0.026 (12)0.036 (11)
Geometric parameters (Å, º) top
S1—C51.744 (3)C3—C41.439 (5)
S1—C61.790 (4)C6—H6A0.9600
O1—C41.265 (4)C6—H6B0.9600
O2—C41.284 (4)C6—H6C0.9600
O2—H20.8200C7—C81.506 (7)
N1—C11.330 (5)C7—H7A0.9700
N1—N21.375 (4)C7—H7B0.9700
N1—C7'1.518 (9)C8—H8A0.9600
N1—C71.522 (6)C8—H8B0.9600
N2—C51.321 (5)C8—H8C0.9600
C1—C31.390 (4)C7'—C8'1.525 (10)
C1—C21.499 (5)C7'—H7'10.9700
C2—H2A0.9600C7'—H7'20.9700
C2—H2B0.9600C8'—H8'10.9600
C2—H2C0.9600C8'—H8'20.9600
C3—C51.415 (5)C8'—H8'30.9600
C5—S1—C6100.31 (18)C3—C5—S1126.3 (3)
C4—O2—H2109.5S1—C6—H6A109.5
C1—N1—N2113.4 (3)S1—C6—H6B109.5
C1—N1—C7'120.7 (6)H6A—C6—H6B109.5
N2—N1—C7'115.3 (6)S1—C6—H6C109.5
C1—N1—C7129.0 (4)H6A—C6—H6C109.5
N2—N1—C7117.0 (4)H6B—C6—H6C109.5
C5—N2—N1104.0 (3)C8—C7—N1103.2 (4)
N1—C1—C3106.1 (3)C8—C7—H7A111.1
N1—C1—C2122.6 (3)N1—C7—H7A111.1
C3—C1—C2131.3 (4)C8—C7—H7B111.1
C1—C2—H2A109.5N1—C7—H7B111.1
C1—C2—H2B109.5H7A—C7—H7B109.1
H2A—C2—H2B109.5N1—C7'—C8'103.8 (9)
C1—C2—H2C109.5N1—C7'—H7'1111.0
H2A—C2—H2C109.5C8'—C7'—H7'1111.0
H2B—C2—H2C109.5N1—C7'—H7'2111.0
C1—C3—C5104.9 (3)C8'—C7'—H7'2111.0
C1—C3—C4128.1 (3)H7'1—C7'—H7'2109.0
C5—C3—C4127.0 (3)C7'—C8'—H8'1109.5
O1—C4—O2122.1 (3)C7'—C8'—H8'2109.5
O1—C4—C3119.3 (3)H8'1—C8'—H8'2109.5
O2—C4—C3118.6 (3)C7'—C8'—H8'3109.5
N2—C5—C3111.5 (3)H8'1—C8'—H8'3109.5
N2—C5—S1122.2 (3)H8'2—C8'—H8'3109.5
C1—N1—N2—C51.5 (5)C5—C3—C4—O2175.2 (3)
C7'—N1—N2—C5146.7 (7)N1—N2—C5—C30.6 (5)
C7—N1—N2—C5170.3 (4)N1—N2—C5—S1177.3 (3)
N2—N1—C1—C31.8 (5)C1—C3—C5—N20.4 (4)
C7'—N1—C1—C3144.9 (7)C4—C3—C5—N2178.6 (3)
C7—N1—C1—C3168.8 (4)C1—C3—C5—S1178.2 (3)
N2—N1—C1—C2179.5 (4)C4—C3—C5—S10.8 (5)
C7'—N1—C1—C236.4 (9)C6—S1—C5—N27.7 (4)
C7—N1—C1—C29.9 (7)C6—S1—C5—C3174.7 (3)
N1—C1—C3—C51.3 (4)C1—N1—C7—C893.0 (6)
C2—C1—C3—C5179.9 (4)N2—N1—C7—C896.6 (5)
N1—C1—C3—C4177.7 (4)C7'—N1—C7—C81.0 (10)
C2—C1—C3—C40.8 (7)C1—N1—C7'—C8'115.4 (11)
C1—C3—C4—O1173.9 (4)N2—N1—C7'—C8'102.2 (11)
C5—C3—C4—O14.9 (5)C7—N1—C7'—C8'0.0 (10)
C1—C3—C4—O26.0 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.821.792.599 (4)169
Symmetry code: (i) x+1, y1, z+1.

Experimental details

Crystal data
Chemical formulaC8H12N2O2S
Mr200.27
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)7.949 (2), 8.330 (2), 8.368 (2)
α, β, γ (°)71.267 (4), 80.761 (5), 74.291 (5)
V3)503.5 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.29
Crystal size (mm)0.22 × 0.18 × 0.12
Data collection
DiffractometerBruker SMART 1000 CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.939, 0.966
No. of measured, independent and
observed [I > 2σ(I)] reflections
2645, 1765, 1253
Rint0.022
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.152, 1.04
No. of reflections1765
No. of parameters142
No. of restraints6
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.35, 0.42

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL.

Selected geometric parameters (Å, º) top
N1—C11.330 (5)C1—C31.390 (4)
N1—N21.375 (4)C3—C51.415 (5)
N2—C51.321 (5)
C1—N1—N2113.4 (3)C1—C3—C5104.9 (3)
C5—N2—N1104.0 (3)N2—C5—C3111.5 (3)
N1—C1—C3106.1 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.821.792.599 (4)169
Symmetry code: (i) x+1, y1, z+1.
 

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds