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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2760–o2761.
Published online 2010 October 9. doi:  10.1107/S1600536810039164
PMCID: PMC3009194

5-Cyclo­hexyl-4-methyl-1H-pyrazol-3(2H)-one monohydrate

Abstract

In the title compound, C10H16N2O·H2O, the cyclo­hexane ring is in a chair conformation and its least-squares plane makes a dihedral angle of 53.68 (5)° with the approximately planar pyrazole ring [maximum deviation = 0.034 (1) Å]. Pairs of inter­molecular N—H(...)O hydrogen bonds form inversion dimers between neighbouring pyrazolone mol­ecules, generating R 2 2(8) ring motifs. The pyrazolone and water mol­ecules are further linked by inter­molecular N—H(...)O, C—H(...)O and O—H(...)O hydrogen bonds into two-dimensional sheets parallel to the bc plane.

Related literature

For pyrazole derivatives and their microbial activities, see: Ragavan et al. (2009 [triangle], 2010 [triangle]). For related structures, see: Shahani et al. (2009 [triangle], 2010a [triangle],b [triangle],c [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-o2760-scheme1.jpg

Experimental

Crystal data

  • C10H16N2O·H2O
  • M r = 198.26
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2760-efi1.jpg
  • a = 13.4959 (3) Å
  • b = 6.2497 (1) Å
  • c = 13.9268 (3) Å
  • β = 112.782 (1)°
  • V = 1083.02 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 100 K
  • 0.46 × 0.27 × 0.23 mm

Data collection

  • Bruker SMART APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.962, T max = 0.981
  • 26403 measured reflections
  • 4715 independent reflections
  • 3863 reflections with I > 2σ(I)
  • R int = 0.033

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.117
  • S = 1.03
  • 4715 reflections
  • 199 parameters
  • All H-atom parameters refined
  • Δρmax = 0.55 e Å−3
  • Δρmin = −0.28 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/S1600536810039164/is2608sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810039164/is2608Isup2.hkl

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

Acknowledgments

HKF and TS thank Universiti Sains Malaysia (USM) for the Research University Grant (grant No. 1001/PFIZIK/811160). TS also thanks USM for the award of a research fellowship. VV is grateful to the 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 used in clinical practice as anti-microbial agents. However, the existence of azole-resistant strains had led to the development of new antimicrobial compounds. In particular, pyrazole derivatives are also extensively studied and used as antimicrobial agents. Pyrazole is an important class of heterocyclic compound and many pyrazole derivatives are reported to have the broad spectrum of biological activities, such as anti-inflammatory, antifungal, herbicidal, anti-tumour, cytotoxic 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 on 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 asymmetric unit of the title compound, (Fig. 1), consists of one 5-cyclohexyl-4-methyl-1H-pyrazol-3(2H)-one molecule (C1—C10/N1/N2/O1) and one water molecule. The 3-cyclohexyl-4-methyl-1 H-pyrazol-5-ol undergoes an enol-to-keto tautomerism during the crystallization process (Fig. 2). The cyclohexane ring is in a chair conformation with puckering parameters of Q = 0.5813 (10) Å, Θ = 177.06 (10)° and [var phi] = 164.9 (19)° (Cremer & Pople, 1975), and its least-squares plane is at an angle of 53.68 (5)° with the approximately planar pyrazole ring (C7–C9/N1/N2; maximum deviation of 0.034 (1) Å at atom N2). The bond lengths (Allen et al., 1987) and angles are within normal ranges and comparable to those closely related structures (Shahani et al., 2009, 2010a,b,c)

In the crystal packing (Fig. 3), pairs of intermolecular N2—H1N2···O1 hydrogen bonds (Table 1) form dimers with neighbouring molecules, generating R22(8) ring motifs (Bernstein et al., 1995). The molecules are further linked by intermolecular N1—H1N1···O1W, C5—H5A···O1W, O1W—H1W1···O1 and O1W—H1W2 ···O1 hydrogen bonds (Table 1) into two-dimensional sheets parallel to the bc plane.

Experimental

The compound has been synthesized using the method available in the literature (Ragavan et al., 2010) and recrystallized using the ethanol-chloroform 1:1 mixture. Yield: 77%. m.p.: 205.4–206.2 °C.

Refinement

All H atoms were located in a difference fourier map and were refined freely [refined distances: N—H = 0.889 (14)–0.923 (14) Å, C—H = 0.93 (12)–1.022 (13) Å and O—H = 0.858 (18)–0.888 (17) Å].

Figures

Fig. 1.
The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom numbering scheme.
Fig. 2.
Enol-to-keto tautomerism of the title compound during crystallization process.
Fig. 3.
The crystal packing of the title compound, viewed two-dimensional arrays parallel to the bc plane. Dashed lines indicate hydrogen bonds.

Crystal data

C10H16N2O·H2OF(000) = 432
Mr = 198.26Dx = 1.216 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9296 reflections
a = 13.4959 (3) Åθ = 3.0–34.7°
b = 6.2497 (1) ŵ = 0.09 mm1
c = 13.9268 (3) ÅT = 100 K
β = 112.782 (1)°Block, colourless
V = 1083.02 (4) Å30.46 × 0.27 × 0.23 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer4715 independent reflections
Radiation source: fine-focus sealed tube3863 reflections with I > 2σ(I)
graphiteRint = 0.033
[var phi] and ω scansθmax = 35.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −20→21
Tmin = 0.962, Tmax = 0.981k = −10→10
26403 measured reflectionsl = −21→21

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)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117All H-atom parameters refined
S = 1.03w = 1/[σ2(Fo2) + (0.0623P)2 + 0.2027P] where P = (Fo2 + 2Fc2)/3
4715 reflections(Δ/σ)max < 0.001
199 parametersΔρmax = 0.55 e Å3
0 restraintsΔρmin = −0.28 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
O10.47692 (5)0.58283 (9)0.36443 (4)0.01649 (11)
N10.35298 (5)0.86770 (11)0.49923 (5)0.01570 (12)
N20.43455 (5)0.74179 (11)0.49437 (5)0.01560 (12)
C10.22589 (7)1.31323 (13)0.36124 (7)0.02077 (15)
C20.12483 (7)1.45257 (14)0.33028 (7)0.02375 (16)
C30.07738 (7)1.44773 (14)0.41354 (7)0.02298 (16)
C40.05310 (7)1.21880 (14)0.43594 (7)0.02146 (16)
C50.15219 (7)1.07543 (13)0.46434 (7)0.01902 (14)
C60.19853 (6)1.08190 (12)0.37959 (6)0.01492 (13)
C70.29215 (6)0.93410 (11)0.40136 (5)0.01425 (13)
C80.41832 (6)0.71084 (12)0.39255 (5)0.01420 (13)
C90.32907 (6)0.83939 (12)0.33169 (5)0.01507 (13)
C100.28323 (7)0.85575 (15)0.21552 (6)0.02220 (16)
O1W0.39076 (5)0.38748 (10)0.17409 (5)0.02017 (12)
H1A0.2820 (10)1.3696 (19)0.4284 (10)0.026 (3)*
H1B0.2551 (10)1.319 (2)0.3063 (11)0.030 (3)*
H2A0.0700 (11)1.398 (2)0.2637 (11)0.029 (3)*
H2B0.1410 (11)1.602 (2)0.3181 (11)0.033 (3)*
H3A0.1301 (11)1.516 (2)0.4797 (10)0.028 (3)*
H3B0.0083 (10)1.536 (2)0.3909 (10)0.027 (3)*
H4A−0.0056 (10)1.161 (2)0.3741 (11)0.029 (3)*
H4B0.0270 (10)1.214 (2)0.4932 (10)0.028 (3)*
H5A0.2079 (11)1.124 (2)0.5307 (11)0.032 (3)*
H5B0.1334 (10)0.922 (2)0.4749 (10)0.025 (3)*
H60.1416 (10)1.028 (2)0.3127 (9)0.020 (3)*
H10A0.2285 (15)0.956 (3)0.1918 (15)0.066 (5)*
H10B0.3351 (14)0.891 (3)0.1877 (13)0.053 (5)*
H10C0.2553 (13)0.719 (3)0.1795 (14)0.060 (5)*
H1N10.3647 (11)0.938 (2)0.5581 (11)0.033 (3)*
H1N20.4682 (11)0.646 (2)0.5476 (11)0.034 (3)*
H1W10.4222 (13)0.442 (3)0.2377 (13)0.046 (4)*
H1W20.4323 (13)0.284 (3)0.1729 (13)0.052 (5)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0200 (3)0.0165 (2)0.0143 (2)0.00467 (19)0.00818 (19)0.00135 (18)
N10.0190 (3)0.0166 (3)0.0112 (2)0.0047 (2)0.0057 (2)0.0004 (2)
N20.0187 (3)0.0162 (3)0.0116 (3)0.0051 (2)0.0056 (2)0.0017 (2)
C10.0210 (3)0.0161 (3)0.0261 (4)0.0025 (3)0.0102 (3)0.0048 (3)
C20.0251 (4)0.0165 (3)0.0282 (4)0.0053 (3)0.0088 (3)0.0047 (3)
C30.0227 (4)0.0170 (3)0.0272 (4)0.0040 (3)0.0074 (3)−0.0051 (3)
C40.0197 (3)0.0206 (4)0.0257 (4)0.0018 (3)0.0105 (3)−0.0039 (3)
C50.0208 (3)0.0179 (3)0.0211 (3)0.0028 (3)0.0113 (3)0.0010 (3)
C60.0158 (3)0.0139 (3)0.0145 (3)0.0018 (2)0.0053 (2)−0.0002 (2)
C70.0166 (3)0.0135 (3)0.0122 (3)0.0015 (2)0.0052 (2)0.0010 (2)
C80.0173 (3)0.0138 (3)0.0118 (3)0.0012 (2)0.0060 (2)0.0009 (2)
C90.0180 (3)0.0156 (3)0.0112 (3)0.0034 (2)0.0052 (2)0.0015 (2)
C100.0275 (4)0.0259 (4)0.0118 (3)0.0087 (3)0.0059 (3)0.0024 (3)
O1W0.0246 (3)0.0216 (3)0.0139 (2)0.0035 (2)0.0071 (2)0.0007 (2)

Geometric parameters (Å, °)

O1—C81.2880 (9)C4—C51.5290 (11)
N1—C71.3555 (9)C4—H4A0.985 (14)
N1—N21.3760 (9)C4—H4B0.989 (13)
N1—H1N10.889 (14)C5—C61.5354 (10)
N2—C81.3622 (9)C5—H5A0.986 (14)
N2—H1N20.923 (14)C5—H5B1.020 (13)
C1—C21.5326 (12)C6—C71.4982 (10)
C1—C61.5378 (11)C6—H61.009 (12)
C1—H1A1.012 (13)C7—C91.3836 (10)
C1—H1B0.987 (13)C8—C91.4226 (10)
C2—C31.5267 (13)C9—C101.4953 (11)
C2—H2A0.995 (14)C10—H10A0.93 (2)
C2—H2B0.986 (14)C10—H10B0.948 (17)
C3—C41.5267 (13)C10—H10C0.987 (19)
C3—H3A1.013 (14)O1W—H1W10.888 (17)
C3—H3B1.022 (13)O1W—H1W20.858 (18)
C7—N1—N2108.07 (6)H4A—C4—H4B106.1 (11)
C7—N1—H1N1126.7 (9)C4—C5—C6111.20 (7)
N2—N1—H1N1118.0 (9)C4—C5—H5A109.6 (8)
C8—N2—N1108.86 (6)C6—C5—H5A108.8 (8)
C8—N2—H1N2125.1 (9)C4—C5—H5B110.4 (7)
N1—N2—H1N2119.0 (8)C6—C5—H5B109.5 (7)
C2—C1—C6109.64 (7)H5A—C5—H5B107.3 (11)
C2—C1—H1A109.2 (7)C7—C6—C5113.01 (6)
C6—C1—H1A108.4 (7)C7—C6—C1112.05 (6)
C2—C1—H1B110.0 (8)C5—C6—C1110.36 (6)
C6—C1—H1B110.7 (8)C7—C6—H6105.2 (7)
H1A—C1—H1B108.9 (10)C5—C6—H6108.0 (7)
C3—C2—C1111.37 (7)C1—C6—H6107.9 (7)
C3—C2—H2A108.8 (8)N1—C7—C9109.38 (6)
C1—C2—H2A109.1 (8)N1—C7—C6121.81 (6)
C3—C2—H2B109.6 (8)C9—C7—C6128.78 (7)
C1—C2—H2B110.7 (8)O1—C8—N2122.31 (7)
H2A—C2—H2B107.2 (11)O1—C8—C9130.36 (6)
C2—C3—C4111.10 (7)N2—C8—C9107.32 (6)
C2—C3—H3A109.2 (7)C7—C9—C8105.99 (6)
C4—C3—H3A109.7 (8)C7—C9—C10128.25 (7)
C2—C3—H3B110.8 (7)C8—C9—C10125.68 (7)
C4—C3—H3B109.0 (8)C9—C10—H10A111.8 (12)
H3A—C3—H3B106.9 (11)C9—C10—H10B113.4 (10)
C3—C4—C5111.51 (7)H10A—C10—H10B108.0 (15)
C3—C4—H4A109.1 (8)C9—C10—H10C114.0 (11)
C5—C4—H4A109.8 (8)H10A—C10—H10C108.0 (15)
C3—C4—H4B111.4 (8)H10B—C10—H10C101.0 (14)
C5—C4—H4B108.8 (8)H1W1—O1W—H1W2104.0 (14)
C7—N1—N2—C8−6.34 (8)C5—C6—C7—C9154.47 (8)
C6—C1—C2—C357.93 (10)C1—C6—C7—C9−80.10 (10)
C1—C2—C3—C4−56.21 (10)N1—N2—C8—O1−173.49 (7)
C2—C3—C4—C554.34 (10)N1—N2—C8—C95.81 (8)
C3—C4—C5—C6−54.98 (9)N1—C7—C9—C8−0.75 (9)
C4—C5—C6—C7−176.77 (7)C6—C7—C9—C8−178.70 (7)
C4—C5—C6—C156.89 (9)N1—C7—C9—C10176.30 (8)
C2—C1—C6—C7175.19 (7)C6—C7—C9—C10−1.65 (14)
C2—C1—C6—C5−57.94 (9)O1—C8—C9—C7176.10 (8)
N2—N1—C7—C94.32 (9)N2—C8—C9—C7−3.12 (8)
N2—N1—C7—C6−177.56 (6)O1—C8—C9—C10−1.05 (14)
C5—C6—C7—N1−23.26 (10)N2—C8—C9—C10179.74 (8)
C1—C6—C7—N1102.18 (8)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N1···O1Wi0.889 (14)1.866 (14)2.7513 (9)173.7 (12)
N2—H1N2···O1ii0.924 (14)1.842 (13)2.7552 (9)169.5 (13)
O1W—H1W1···O10.889 (17)1.851 (17)2.7354 (8)173.2 (18)
O1W—H1W2···O1iii0.860 (19)1.961 (19)2.8007 (9)165.0 (16)
C5—H5A···O1Wi0.987 (14)2.503 (15)3.4161 (12)153.7 (11)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2608).

References

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