PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o3020–o3021.
Published online 2010 October 31. doi:  10.1107/S1600536810043886
PMCID: PMC3009126

3-(2,5-Dimethyl­furan-3-yl)-1H-pyrazol-5-ol–ethyl 3-(propan-2-yl­idene)carbazate (1/1)

Abstract

In the title 1:1 adduct, C6H12N2O2·C9H10N2O2, the maximum deviations from the 1H-pyrazole-5-ol and furan rings are 0.014 (1) and 0.003 (1) Å, respectively. The dihedral angle formed between the 1H-pyrazol-5-ol and 2,5-dimethyl­furan rings is 21.07 (5)°. In the crystal, pairs of inter­molecular O—H(...)N hydrogen bonds form inversion dimers of the 3-(2,5-dimethyl­furan-3-yl)-1H-pyrazol-5-ol species, generating R 2 2(8) ring motifs. Mol­ecules are further linked by inter­molecular N—H(...)O, N—H(...)N and C—H(...)O hydrogen bonds to form ribbons along the [010] direction containing bifurcated R 1 2(5) and R 2 1(7) ring motifs. Further stablization of the packing is provided by weak π–π [centroid–centroid distance = 3.5686 (15) Å] and C—H(...)π inter­actions.

Related literature

For pyrazole derivatives and their microbial activities, see: Ragavan et al. (2009 [triangle], 2010 [triangle]). For a related structure, see: Shahani et al. (2010 [triangle]). For ring conformations, see: Cremer & Pople (1975 [triangle]). For hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o3020-scheme1.jpg

Experimental

Crystal data

  • C6H12N2O2·C9H10N2O2
  • M r = 322.37
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3020-efi1.jpg
  • a = 8.6988 (17) Å
  • b = 9.4830 (19) Å
  • c = 11.837 (4) Å
  • α = 107.293 (4)°
  • β = 100.354 (5)°
  • γ = 108.346 (3)°
  • V = 843.7 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 100 K
  • 0.40 × 0.21 × 0.13 mm

Data collection

  • Bruker APEXII DUO CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.964, T max = 0.988
  • 13322 measured reflections
  • 3264 independent reflections
  • 2911 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.033
  • wR(F 2) = 0.099
  • S = 1.11
  • 3264 reflections
  • 225 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.29 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810043886/hb5696sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810043886/hb5696Isup2.hkl

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

Acknowledgments

H-KF and TS thank Universiti Sains Malaysia (USM) for the Research University Grant No. 1001/PFIZIK/811160. TS also thanks USM for the award of a research fellowship. VV is grateful to DST–India for funding through the Young Scientist Scheme (Fast Track Proposal).

supplementary crystallographic information

Comment

Antibacterial and antifungal activities of the azoles are most widely studied and some of them are in clinical practice as anti-microbial agents. However, the azole-resistant strain had led to the development of new antimicrobial compounds. In particular, pyrazole derivatives are extensively studied and used as antimicrobial agents. Pyrazole is an important class of heterocyclic compounds and many pyrazole derivatives are reported to have the broad spectrum of biological properties such as anti-inflammatory, antifungal, herbicidal, anti-tumour, cytotoxic, molecular modelling and antiviral activities. Pyrazole derivatives also act as antiangiogenic agents, A3 adenosine receptor antagonists, neuropeptide YY5 receptor antagonists, kinase inhibitor for treatment of type 2 diabetes, hyperlipidemia, obesity, and thrombopiotinmimetics. Recently urea derivatives of pyrazoles have been reported as potent inhibitors of p38 kinase. Since the high electronegativity of halogens (particularly chlorine and fluorine) in the aromatic part of the drug molecules play an important role in enhancing their biological activity, we are interested to have 4-fluoro or 4-chloro substitution in the aryls of 1,5-diaryl pyrazoles. As part of our on-going research aiming the synthesis of new antimicrobial compounds, we have reported the synthesis of novel pyrazole derivatives and their microbial activities (Ragavan et al., 2009; 2010). The structure of the title compound is presented here.

The asymmetric unit of the title compound, (Fig. 1), consists of one 3-(2,5-dimethylfuran-3-yl)-1H-pyrazol-5-ol and one ethyl2- (propan-2-ylidene)hydrazine carboxylate. The maximum deviations in 1H- pyrazole-5-ol (N1/N2/C1–C3/O2) and furan (C4–C7/O1) rings are 0.014 (1) and 0.003 (1) Å at atoms C2 and C7, respectively. The dihedral angles formed between the 1H-pyrazole-5-ol ring and 2,5-dimethylfuran ring (C4–C9/O1) is 21.07 (5)°. The bond lengths (Allen et al.,1987) and angles are within normal ranges and comparable to those closely related structures (Shahani et al., 2010).

In the crystal packing (Fig. 2), pairs of intermolecular N2—H1O2···O2 hydrogen bonds form dimers with neighbouring molecules, generating R22(8) ring motif. Furthermore N1—H1N1···O4, N1—H1N1···N4, N3—H1N3···O2, O2—H1O2···N2 and C5—H5A···O4 hydrogen bonds (Table 1) link the molecules into ribbons along [010] direction with bifurcated R12(5) and R21(7) ring motifs. The crystal structure is stablilized by weak π–π and C—H···π interactions.interactions [cg1···cg1=3.5686 (15) Å, symmetry code, 2-X, 1-Y, –Z], cg1 is the centroids of the 1H-pyrazole ring (N1/N2/C1—C3) and cg2 is the centroids of the 1H-pyrazole ring (N1/N2/C1–C3).

Experimental

The compound has been synthesized using the method available in the literature (Ragavan et al.,2009) and recrystallized using the ethanol-chloroform 1:1 mixture to yield colourless blocks of (I). Yield: 78%. M.pt: 225.5–227.5 °C.

Refinement

The hydrogen atoms bound to C atoms were positioned geometrically [C–H = 0.96–0.97 Å] with Uiso(H) =1.2 or 1.5Uiso(C). A rotating group model was applied to the methyl groups. The hydrogen atoms attached to the N and O atoms were located from the difference map and refined freely, [N–H = 0.872 (18)–0.883 (18) Å, O–H = 0.93 Å].

Figures

Fig. 1.
The molecular structure of the title compound, showing 50% probability displacement ellipsoids.
Fig. 2.
The crystal packing of the title compound, viewed along c axis, showing ribbons along the [010] direction..

Crystal data

C6H12N2O2·C9H10N2O2Z = 2
Mr = 322.37F(000) = 344
Triclinic, P1Dx = 1.269 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.6988 (17) ÅCell parameters from 7782 reflections
b = 9.4830 (19) Åθ = 2.6–31.7°
c = 11.837 (4) ŵ = 0.09 mm1
α = 107.293 (4)°T = 100 K
β = 100.354 (5)°Block, colourless
γ = 108.346 (3)°0.40 × 0.21 × 0.13 mm
V = 843.7 (3) Å3

Data collection

Bruker APEXII DUO CCD diffractometer3264 independent reflections
Radiation source: fine-focus sealed tube2911 reflections with I > 2σ(I)
graphiteRint = 0.026
[var phi] and ω scansθmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −10→10
Tmin = 0.964, Tmax = 0.988k = −11→11
13322 measured reflectionsl = −14→14

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H atoms treated by a mixture of independent and constrained refinement
S = 1.11w = 1/[σ2(Fo2) + (0.045P)2 + 0.2939P] where P = (Fo2 + 2Fc2)/3
3264 reflections(Δ/σ)max < 0.001
225 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = −0.22 e Å3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.
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)

xyzUiso*/Ueq
O10.72298 (12)0.49965 (12)−0.03577 (8)0.0272 (2)
O21.41202 (12)1.13027 (10)0.43430 (9)0.0232 (2)
N11.21447 (13)0.71967 (13)0.29969 (10)0.0197 (2)
N21.34466 (13)0.85605 (12)0.38574 (9)0.0190 (2)
C11.31074 (15)0.97528 (15)0.36573 (11)0.0185 (3)
C21.16205 (16)0.91874 (15)0.26795 (12)0.0211 (3)
H2A1.11360.97910.23660.025*
C31.10286 (15)0.75316 (15)0.22806 (11)0.0185 (3)
C40.95185 (16)0.62751 (15)0.13126 (11)0.0201 (3)
C50.87164 (16)0.46384 (15)0.11997 (12)0.0222 (3)
H5A0.90760.41690.17250.027*
C60.73478 (17)0.39202 (16)0.01874 (12)0.0252 (3)
C70.85745 (16)0.64286 (16)0.03429 (12)0.0240 (3)
C80.8742 (2)0.77483 (18)−0.01199 (14)0.0344 (3)
H8A0.99220.84140.00890.052*
H8B0.81660.83820.02570.052*
H8C0.82460.7301−0.10050.052*
C90.59939 (19)0.22804 (18)−0.04258 (14)0.0342 (3)
H9A0.61860.16320.00270.051*
H9B0.60110.1810−0.12600.051*
H9C0.49090.2338−0.04410.051*
O30.08857 (11)0.22838 (11)0.42456 (9)0.0236 (2)
O40.06433 (11)0.42612 (11)0.36063 (9)0.0244 (2)
N30.29597 (14)0.35988 (13)0.36500 (10)0.0209 (2)
N40.37772 (13)0.48909 (12)0.33504 (10)0.0201 (2)
C10−0.21443 (18)0.07821 (18)0.31978 (15)0.0346 (3)
H10A−0.32330.04710.33380.052*
H10B−0.1904−0.01530.28710.052*
H10C−0.21540.13020.26150.052*
C11−0.07996 (17)0.19197 (17)0.44018 (13)0.0267 (3)
H11A−0.09840.29050.46950.032*
H11B−0.08780.14430.50210.032*
C120.14196 (16)0.34622 (14)0.38212 (11)0.0194 (3)
C130.52197 (16)0.50193 (15)0.31731 (11)0.0212 (3)
C140.60676 (18)0.38865 (18)0.32513 (14)0.0300 (3)
H14A0.61550.37770.40390.045*
H14B0.71830.42990.31690.045*
H14C0.54080.28560.25960.045*
C150.61073 (17)0.64131 (16)0.28562 (13)0.0249 (3)
H15A0.54360.70440.28430.037*
H15B0.62590.60250.20540.037*
H15C0.71960.70630.34680.037*
H1N11.211 (2)0.626 (2)0.3012 (15)0.033 (4)*
H1N30.347 (2)0.304 (2)0.3897 (15)0.031 (4)*
H1O21.496 (3)1.138 (2)0.500 (2)0.057 (6)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0228 (5)0.0284 (5)0.0227 (5)0.0062 (4)0.0009 (4)0.0068 (4)
O20.0222 (5)0.0154 (4)0.0274 (5)0.0068 (4)−0.0018 (4)0.0078 (4)
N10.0200 (5)0.0146 (5)0.0221 (5)0.0065 (4)0.0026 (4)0.0061 (4)
N20.0178 (5)0.0157 (5)0.0215 (5)0.0065 (4)0.0028 (4)0.0061 (4)
C10.0190 (6)0.0173 (6)0.0212 (6)0.0085 (5)0.0067 (5)0.0080 (5)
C20.0209 (6)0.0212 (6)0.0231 (6)0.0115 (5)0.0041 (5)0.0090 (5)
C30.0174 (6)0.0216 (6)0.0187 (6)0.0095 (5)0.0070 (5)0.0079 (5)
C40.0190 (6)0.0218 (6)0.0194 (6)0.0090 (5)0.0073 (5)0.0059 (5)
C50.0215 (6)0.0224 (6)0.0217 (6)0.0084 (5)0.0074 (5)0.0069 (5)
C60.0233 (7)0.0258 (7)0.0243 (7)0.0080 (5)0.0089 (5)0.0073 (5)
C70.0211 (6)0.0246 (7)0.0221 (6)0.0075 (5)0.0043 (5)0.0060 (5)
C80.0364 (8)0.0329 (8)0.0294 (7)0.0115 (7)−0.0003 (6)0.0139 (6)
C90.0279 (7)0.0295 (8)0.0323 (8)0.0019 (6)0.0049 (6)0.0067 (6)
O30.0212 (5)0.0240 (5)0.0319 (5)0.0101 (4)0.0109 (4)0.0159 (4)
O40.0234 (5)0.0235 (5)0.0314 (5)0.0129 (4)0.0088 (4)0.0133 (4)
N30.0214 (5)0.0195 (5)0.0282 (6)0.0108 (5)0.0090 (4)0.0139 (5)
N40.0217 (5)0.0185 (5)0.0218 (5)0.0084 (4)0.0064 (4)0.0093 (4)
C100.0259 (7)0.0307 (8)0.0430 (9)0.0076 (6)0.0118 (6)0.0112 (7)
C110.0232 (7)0.0288 (7)0.0340 (7)0.0104 (6)0.0152 (6)0.0156 (6)
C120.0218 (6)0.0168 (6)0.0187 (6)0.0079 (5)0.0045 (5)0.0063 (5)
C130.0221 (6)0.0226 (6)0.0196 (6)0.0100 (5)0.0061 (5)0.0079 (5)
C140.0310 (7)0.0334 (8)0.0411 (8)0.0207 (6)0.0195 (6)0.0215 (7)
C150.0234 (7)0.0261 (7)0.0293 (7)0.0108 (5)0.0100 (5)0.0138 (6)

Geometric parameters (Å, °)

O1—C71.3719 (16)C9—H9C0.9600
O1—C61.3792 (17)O3—C121.3445 (15)
O2—C11.3468 (15)O3—C111.4558 (15)
O2—H1O20.93 (2)O4—C121.2124 (15)
N1—C31.3493 (16)N3—C121.3625 (17)
N1—N21.3685 (14)N3—N41.3905 (15)
N1—H1N10.883 (18)N3—H1N30.872 (18)
N2—C11.3288 (16)N4—C131.2834 (17)
C1—C21.3988 (18)C10—C111.502 (2)
C2—C31.3844 (18)C10—H10A0.9600
C2—H2A0.9300C10—H10B0.9600
C3—C41.4561 (18)C10—H10C0.9600
C4—C71.3597 (19)C11—H11A0.9700
C4—C51.4405 (18)C11—H11B0.9700
C5—C61.3448 (19)C13—C141.4967 (19)
C5—H5A0.9300C13—C151.4967 (18)
C6—C91.4835 (19)C14—H14A0.9600
C7—C81.486 (2)C14—H14B0.9600
C8—H8A0.9600C14—H14C0.9600
C8—H8B0.9600C15—H15A0.9600
C8—H8C0.9600C15—H15B0.9600
C9—H9A0.9600C15—H15C0.9600
C9—H9B0.9600
C7—O1—C6107.17 (10)H9A—C9—H9C109.5
C1—O2—H1O2110.5 (13)H9B—C9—H9C109.5
C3—N1—N2111.95 (10)C12—O3—C11115.88 (10)
C3—N1—H1N1129.8 (11)C12—N3—N4116.20 (11)
N2—N1—H1N1118.1 (11)C12—N3—H1N3119.0 (11)
C1—N2—N1104.49 (10)N4—N3—H1N3123.2 (11)
N2—C1—O2121.83 (11)C13—N4—N3116.67 (11)
N2—C1—C2111.95 (11)C11—C10—H10A109.5
O2—C1—C2126.22 (11)C11—C10—H10B109.5
C3—C2—C1104.84 (11)H10A—C10—H10B109.5
C3—C2—H2A127.6C11—C10—H10C109.5
C1—C2—H2A127.6H10A—C10—H10C109.5
N1—C3—C2106.77 (11)H10B—C10—H10C109.5
N1—C3—C4122.08 (11)O3—C11—C10110.77 (11)
C2—C3—C4131.15 (12)O3—C11—H11A109.5
C7—C4—C5106.49 (11)C10—C11—H11A109.5
C7—C4—C3126.43 (12)O3—C11—H11B109.5
C5—C4—C3127.08 (12)C10—C11—H11B109.5
C6—C5—C4106.74 (12)H11A—C11—H11B108.1
C6—C5—H5A126.6O4—C12—O3125.45 (12)
C4—C5—H5A126.6O4—C12—N3125.31 (12)
C5—C6—O1109.97 (12)O3—C12—N3109.22 (10)
C5—C6—C9134.00 (13)N4—C13—C14125.22 (12)
O1—C6—C9116.02 (12)N4—C13—C15116.82 (12)
C4—C7—O1109.62 (12)C14—C13—C15117.96 (11)
C4—C7—C8134.17 (13)C13—C14—H14A109.5
O1—C7—C8116.15 (11)C13—C14—H14B109.5
C7—C8—H8A109.5H14A—C14—H14B109.5
C7—C8—H8B109.5C13—C14—H14C109.5
H8A—C8—H8B109.5H14A—C14—H14C109.5
C7—C8—H8C109.5H14B—C14—H14C109.5
H8A—C8—H8C109.5C13—C15—H15A109.5
H8B—C8—H8C109.5C13—C15—H15B109.5
C6—C9—H9A109.5H15A—C15—H15B109.5
C6—C9—H9B109.5C13—C15—H15C109.5
H9A—C9—H9B109.5H15A—C15—H15C109.5
C6—C9—H9C109.5H15B—C15—H15C109.5
C3—N1—N2—C10.09 (13)C7—O1—C6—C50.06 (14)
N1—N2—C1—O2179.58 (11)C7—O1—C6—C9179.60 (11)
N1—N2—C1—C2−0.44 (14)C5—C4—C7—O10.55 (14)
N2—C1—C2—C30.62 (14)C3—C4—C7—O1−178.68 (11)
O2—C1—C2—C3−179.40 (11)C5—C4—C7—C8−176.26 (16)
N2—N1—C3—C20.30 (14)C3—C4—C7—C84.5 (2)
N2—N1—C3—C4−178.86 (10)C6—O1—C7—C4−0.39 (14)
C1—C2—C3—N1−0.53 (13)C6—O1—C7—C8177.06 (12)
C1—C2—C3—C4178.51 (12)C12—N3—N4—C13−179.21 (11)
N1—C3—C4—C7−161.23 (13)C12—O3—C11—C1084.10 (14)
C2—C3—C4—C719.8 (2)C11—O3—C12—O42.70 (18)
N1—C3—C4—C519.70 (19)C11—O3—C12—N3−176.27 (10)
C2—C3—C4—C5−159.23 (13)N4—N3—C12—O48.26 (18)
C7—C4—C5—C6−0.50 (14)N4—N3—C12—O3−172.77 (10)
C3—C4—C5—C6178.72 (12)N3—N4—C13—C140.65 (19)
C4—C5—C6—O10.27 (14)N3—N4—C13—C15−179.72 (11)
C4—C5—C6—C9−179.15 (15)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N1···O4i0.883 (18)2.304 (19)3.0363 (19)140.1 (16)
N1—H1N1···N4i0.883 (18)2.288 (19)3.043 (2)143.1 (16)
N3—H1N3···O2ii0.872 (18)2.076 (19)2.9293 (19)166.7 (18)
O2—H1O2···N2iii0.93 (2)1.73 (2)2.6602 (17)176 (2)
C5—H5A···O4i0.932.353.212 (2)153
C11—H11B···Cg2iv0.972.713.498 (20)138

Symmetry codes: (i) x+1, y, z; (ii) x−1, y−1, z; (iii) −x+3, −y+2, −z+1; (iv) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5696).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555–1573.
  • Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wiscosin, USA.
  • Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst.19, 105–107.
  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc.97, 1354–1358.
  • Ragavan, R. V., Vijayakumar, V. & Kumari, N. S. (2009). Eur. J. Med. Chem.44, 3852–3857. [PubMed]
  • Ragavan, R. V., Vijayakumar, V. & Kumari, N. S. (2010). Eur. J. Med. Chem.45, 1173–1180. [PubMed]
  • Shahani, T., Fun, H.-K., Ragavan, R. V., Vijayakumar, V. & Venkatesh, M. (2010). Acta Cryst. E66, o2815–o2816. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography