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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1848.
Published online 2010 June 26. doi:  10.1107/S1600536810024281
PMCID: PMC3006733

rac-5-Acetyl-6-hy­droxy-3,6-dimethyl-4-phenyl-2H-4,5,6,7-tetra­hydro­indazol-1-ium chloride

Abstract

The structure of the title compound, C17H21N2O2 +·Cl, is of inter­est with respect to its biological activity. The title compound comprises an organic cation and a chloride anion in the asymmetric unit. The positive charge is localized in a pyrazole moiety forming a pyrazolium cation. The structure displays inter­molecular O—H(...)Cl and N—H(...)Cl hydrogen bonding.

Related literature

For general background, see: Raptis et al. (1993 [triangle]); Rabe (1904 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1848-scheme1.jpg

Experimental

Crystal data

  • C17H21N2O2 +·Cl
  • M r = 320.81
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1848-efi1.jpg
  • a = 6.9661 (3) Å
  • b = 8.3527 (4) Å
  • c = 15.6739 (7) Å
  • α = 88.145 (1)°
  • β = 87.385 (1)°
  • γ = 67.882 (1)°
  • V = 843.89 (7) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.24 mm−1
  • T = 296 K
  • 0.30 × 0.30 × 0.20 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003 [triangle]) T min = 0.933, T max = 0.955
  • 9861 measured reflections
  • 4188 independent reflections
  • 3279 reflections with I > 2σ(I)
  • R int = 0.015

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.130
  • S = 1.00
  • 4188 reflections
  • 199 parameters
  • H-atom parameters constrained
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT-Plus (Bruker, 2001 [triangle]); data reduction: SAINT-Plus; 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.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810024281/kp2265sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810024281/kp2265Isup2.hkl

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

Acknowledgments

We thank Professor Abel M. Maharramov for fruitful discussions and help with this work.

supplementary crystallographic information

Comment

(rac)-5-Acetyl-6-hydroxy-3,6-dimethyl-4-phenyl-2H-4,5,6,7- tetrahyroindazolium chloride (I) have good antibacterial and biological properties. We have synthesised the title compound, (I), and its structure is reported here (Fig. 1). The two [(C2(R),C4(R)] of three stereogenic centres of tetrahydroindazole moiety are of the same chirality. As the crystal crystallises in the centrosymmetric space group, the racemate (1:1) is present. The crystal structure involves O—H···Cl, and N—H···C intermolecular hydrogen bonds (Table 1 and Fig. 2).

Experimental

2,4-Diacetyl-5-hydroxy-5-methyl-3-phenylcyclohexanon (20 mmol)and hydrazine hydrate (20 mmol) were dissolved in 20 ml ethanol. The mixture was stirred at 340 K within 10 h. Through suspension in absolute toluene a flow of dry gaseous hydrogen chloride was used at 278-283 K. From a solution a white solid was obtained. A crude product was filtered and washed with ethanol. Then, the crude product was dissolved in ethanol (50 ml) and recrystallised to yield colourless block-shaped crystals of (I).

Refinement

The hydrogen atoms of the OH and NH-groups of the molecule (I) were localized in a difference-Fourier map and included in the refinement with fixed positional and isotropic displacement parameters [Uiso (H) = 1.5Ueq(C) for CH3-group and Uiso(H) = 1.2Ueq(N) for amino groups]. The other hydrogen atoms were placed in calculated positions with and refined in the riding model with fixed isotropic displacement parameters [Uiso(H) = 1.2Ueq(C)]. 24 reflections, with experimentally observed F2 deviating significantly from the theoretically calculated F2, were omitted from the refinement. Moreover, 76 reflections were not measured because the angle limits.

Figures

Fig. 1.
The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
Fig. 2.
A hydrogen-bonded (dashed lines) ribbon in the title compound. H atoms not involved in hydrogen bonding have been omitted for clarity.

Crystal data

C17H21N2O2+·ClZ = 2
Mr = 320.81F(000) = 340
Triclinic, P1Dx = 1.263 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.9661 (3) ÅCell parameters from 4494 reflections
b = 8.3527 (4) Åθ = 2.6–28.3°
c = 15.6739 (7) ŵ = 0.24 mm1
α = 88.145 (1)°T = 296 K
β = 87.385 (1)°Prism, colourless
γ = 67.882 (1)°0.30 × 0.30 × 0.20 mm
V = 843.89 (7) Å3

Data collection

Bruker APEXII CCD diffractometer4188 independent reflections
Radiation source: fine-focus sealed tube3279 reflections with I > 2σ(I)
graphiteRint = 0.015
[var phi] and ω scansθmax = 28.4°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)h = −9→9
Tmin = 0.933, Tmax = 0.955k = −11→11
9861 measured reflectionsl = −20→20

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)] = 0.043Hydrogen site location: difference Fourier map
wR(F2) = 0.130H-atom parameters constrained
S = 1.00w = 1/[σ2(Fo2) + (0.0702P)2 + 0.1788P] where P = (Fo2 + 2Fc2)/3
4188 reflections(Δ/σ)max < 0.001
199 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = −0.23 e Å3

Special details

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
Cl0.79637 (7)0.21601 (6)0.42366 (3)0.06850 (18)
O10.82690 (19)0.50419 (14)0.28900 (7)0.0544 (3)
H1A0.82560.42950.32400.082*
C20.6910 (2)0.84494 (17)0.21715 (8)0.0370 (3)
H2A0.66540.76340.18010.044*
C70.6848 (2)1.00157 (18)0.16319 (9)0.0403 (3)
C30.9075 (2)0.75279 (17)0.25585 (9)0.0407 (3)
H3A0.94150.84180.28350.049*
C1A0.5285 (2)0.89218 (18)0.28808 (9)0.0408 (3)
O21.2259 (2)0.71271 (18)0.18122 (10)0.0707 (4)
N20.2393 (2)0.9911 (2)0.36527 (10)0.0608 (4)
H2B0.11141.04410.38080.073*
C10.3197 (2)0.99656 (19)0.28640 (10)0.0469 (3)
C131.0750 (2)0.67523 (19)0.18596 (10)0.0475 (3)
C80.6566 (2)1.1566 (2)0.20107 (11)0.0484 (3)
H8A0.64421.16420.26030.058*
C5A0.5664 (3)0.8269 (2)0.37032 (9)0.0497 (4)
N10.3884 (3)0.8905 (2)0.41623 (9)0.0626 (4)
H1B0.37220.87030.46970.075*
C60.1911 (2)1.0995 (2)0.21689 (12)0.0557 (4)
H6A0.05081.15620.23810.084*
H6B0.19421.02470.17120.084*
H6C0.24451.18450.19620.084*
C40.9097 (3)0.6160 (2)0.32611 (9)0.0483 (3)
C120.7041 (3)0.9940 (3)0.07526 (11)0.0643 (5)
H12A0.72160.89160.04830.077*
C90.6467 (3)1.3007 (2)0.15225 (14)0.0623 (5)
H9A0.62541.40450.17870.075*
C141.0503 (3)0.5535 (2)0.12344 (12)0.0611 (4)
H14A1.16750.51740.08390.092*
H14B0.92590.61070.09280.092*
H14C1.04160.45430.15350.092*
C50.7689 (3)0.7091 (2)0.40209 (10)0.0577 (4)
H5A0.74870.62500.44190.069*
H5B0.83350.77460.43180.069*
C151.1284 (3)0.5161 (3)0.35650 (13)0.0697 (5)
H15A1.12450.43360.39990.104*
H15B1.18240.59520.37950.104*
H15C1.21600.45680.30920.104*
C110.6976 (4)1.1385 (3)0.02648 (13)0.0857 (7)
H11A0.71351.1313−0.03270.103*
C100.6680 (3)1.2903 (3)0.06526 (15)0.0771 (6)
H10A0.66241.38670.03250.092*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl0.0681 (3)0.0699 (3)0.0529 (2)−0.0135 (2)0.0232 (2)0.0174 (2)
O10.0784 (8)0.0446 (6)0.0443 (6)−0.0286 (6)−0.0005 (5)0.0089 (4)
C20.0406 (7)0.0392 (6)0.0305 (6)−0.0150 (5)0.0049 (5)0.0008 (5)
C70.0331 (6)0.0466 (7)0.0376 (6)−0.0120 (5)0.0024 (5)0.0094 (5)
C30.0458 (7)0.0372 (6)0.0379 (6)−0.0148 (6)0.0001 (5)0.0027 (5)
C1A0.0477 (7)0.0400 (7)0.0371 (6)−0.0202 (6)0.0090 (5)−0.0008 (5)
O20.0494 (7)0.0660 (8)0.0957 (10)−0.0224 (6)0.0128 (6)0.0015 (7)
N20.0598 (8)0.0617 (8)0.0610 (8)−0.0257 (7)0.0290 (7)−0.0075 (7)
C10.0488 (8)0.0423 (7)0.0520 (8)−0.0216 (6)0.0165 (6)−0.0059 (6)
C130.0442 (7)0.0380 (7)0.0539 (8)−0.0096 (6)0.0047 (6)0.0090 (6)
C80.0455 (8)0.0493 (8)0.0530 (8)−0.0212 (6)−0.0043 (6)0.0093 (6)
C5A0.0667 (10)0.0497 (8)0.0354 (7)−0.0265 (7)0.0129 (6)−0.0014 (6)
N10.0789 (10)0.0658 (9)0.0437 (7)−0.0307 (8)0.0246 (7)−0.0027 (6)
C60.0420 (8)0.0487 (8)0.0718 (11)−0.0128 (7)0.0071 (7)0.0005 (7)
C40.0620 (9)0.0437 (7)0.0372 (7)−0.0179 (7)−0.0044 (6)0.0075 (6)
C120.0766 (12)0.0636 (10)0.0398 (8)−0.0138 (9)0.0079 (8)0.0095 (7)
C90.0492 (9)0.0508 (9)0.0895 (13)−0.0225 (7)−0.0095 (8)0.0199 (9)
C140.0675 (11)0.0518 (9)0.0554 (9)−0.0145 (8)0.0176 (8)−0.0058 (7)
C50.0796 (11)0.0598 (10)0.0326 (7)−0.0256 (9)0.0001 (7)0.0065 (6)
C150.0735 (12)0.0644 (11)0.0615 (11)−0.0147 (9)−0.0182 (9)0.0181 (9)
C110.0979 (16)0.0927 (16)0.0494 (10)−0.0205 (13)0.0106 (10)0.0316 (11)
C100.0620 (11)0.0730 (13)0.0880 (14)−0.0198 (10)−0.0012 (10)0.0454 (12)

Geometric parameters (Å, °)

O1—C41.419 (2)C5A—C51.481 (3)
O1—H1A0.8200N1—H1B0.8600
C2—C1A1.5001 (18)C6—H6A0.9600
C2—C71.5224 (18)C6—H6B0.9600
C2—C31.5535 (19)C6—H6C0.9600
C2—H2A0.9800C4—C151.526 (2)
C7—C121.380 (2)C4—C51.537 (2)
C7—C81.384 (2)C12—C111.395 (3)
C3—C131.530 (2)C12—H12A0.9300
C3—C41.5573 (19)C9—C101.367 (3)
C3—H3A0.9800C9—H9A0.9300
C1A—C5A1.380 (2)C14—H14A0.9600
C1A—C11.387 (2)C14—H14B0.9600
O2—C131.203 (2)C14—H14C0.9600
N2—C11.3404 (19)C5—H5A0.9700
N2—N11.341 (2)C5—H5B0.9700
N2—H2B0.8600C15—H15A0.9600
C1—C61.476 (2)C15—H15B0.9600
C13—C141.495 (2)C15—H15C0.9600
C8—C91.386 (2)C11—C101.364 (4)
C8—H8A0.9300C11—H11A0.9300
C5A—N11.336 (2)C10—H10A0.9300
C4—O1—H1A109.5C1—C6—H6C109.5
C1A—C2—C7112.15 (11)H6A—C6—H6C109.5
C1A—C2—C3109.00 (11)H6B—C6—H6C109.5
C7—C2—C3110.88 (11)O1—C4—C15111.19 (14)
C1A—C2—H2A108.2O1—C4—C5109.66 (14)
C7—C2—H2A108.2C15—C4—C5109.42 (14)
C3—C2—H2A108.2O1—C4—C3106.27 (11)
C12—C7—C8118.09 (14)C15—C4—C3111.47 (14)
C12—C7—C2121.10 (14)C5—C4—C3108.75 (12)
C8—C7—C2120.80 (12)C7—C12—C11120.6 (2)
C13—C3—C2111.19 (11)C7—C12—H12A119.7
C13—C3—C4111.65 (11)C11—C12—H12A119.7
C2—C3—C4112.95 (12)C10—C9—C8119.94 (19)
C13—C3—H3A106.9C10—C9—H9A120.0
C2—C3—H3A106.9C8—C9—H9A120.0
C4—C3—H3A106.9C13—C14—H14A109.5
C5A—C1A—C1106.91 (13)C13—C14—H14B109.5
C5A—C1A—C2123.23 (14)H14A—C14—H14B109.5
C1—C1A—C2129.81 (13)C13—C14—H14C109.5
C1—N2—N1109.73 (14)H14A—C14—H14C109.5
C1—N2—H2B125.1H14B—C14—H14C109.5
N1—N2—H2B125.1C5A—C5—C4109.23 (12)
N2—C1—C1A106.79 (14)C5A—C5—H5A109.8
N2—C1—C6121.61 (14)C4—C5—H5A109.8
C1A—C1—C6131.60 (13)C5A—C5—H5B109.8
O2—C13—C14120.14 (15)C4—C5—H5B109.8
O2—C13—C3120.00 (15)H5A—C5—H5B108.3
C14—C13—C3119.86 (14)C4—C15—H15A109.5
C7—C8—C9121.12 (16)C4—C15—H15B109.5
C7—C8—H8A119.4H15A—C15—H15B109.5
C9—C8—H8A119.4C4—C15—H15C109.5
N1—C5A—C1A107.79 (15)H15A—C15—H15C109.5
N1—C5A—C5126.19 (14)H15B—C15—H15C109.5
C1A—C5A—C5126.01 (14)C10—C11—C12120.22 (19)
C5A—N1—N2108.77 (13)C10—C11—H11A119.9
C5A—N1—H1B125.6C12—C11—H11A119.9
N2—N1—H1B125.6C11—C10—C9120.03 (17)
C1—C6—H6A109.5C11—C10—H10A120.0
C1—C6—H6B109.5C9—C10—H10A120.0
H6A—C6—H6B109.5
C1A—C2—C7—C12−137.04 (15)C1—C1A—C5A—N1−0.54 (17)
C3—C2—C7—C12100.85 (16)C2—C1A—C5A—N1−178.05 (13)
C1A—C2—C7—C842.07 (18)C1—C1A—C5A—C5−179.78 (15)
C3—C2—C7—C8−80.04 (15)C2—C1A—C5A—C52.7 (2)
C1A—C2—C3—C13170.59 (11)C1A—C5A—N1—N21.10 (19)
C7—C2—C3—C13−65.48 (14)C5—C5A—N1—N2−179.66 (16)
C1A—C2—C3—C444.16 (15)C1—N2—N1—C5A−1.26 (19)
C7—C2—C3—C4168.09 (11)C13—C3—C4—O1−72.98 (16)
C7—C2—C1A—C5A−136.73 (14)C2—C3—C4—O153.21 (15)
C3—C2—C1A—C5A−13.55 (19)C13—C3—C4—C1548.32 (18)
C7—C2—C1A—C146.4 (2)C2—C3—C4—C15174.51 (13)
C3—C2—C1A—C1169.55 (14)C13—C3—C4—C5169.05 (13)
N1—N2—C1—C1A0.90 (18)C2—C3—C4—C5−64.77 (16)
N1—N2—C1—C6−179.36 (15)C8—C7—C12—C110.7 (3)
C5A—C1A—C1—N2−0.21 (17)C2—C7—C12—C11179.84 (18)
C2—C1A—C1—N2177.07 (14)C7—C8—C9—C10−1.0 (2)
C5A—C1A—C1—C6−179.92 (16)N1—C5A—C5—C4159.56 (16)
C2—C1A—C1—C6−2.6 (3)C1A—C5A—C5—C4−21.3 (2)
C2—C3—C13—O2125.03 (16)O1—C4—C5—C5A−66.44 (16)
C4—C3—C13—O2−107.83 (16)C15—C4—C5—C5A171.35 (15)
C2—C3—C13—C14−54.72 (17)C3—C4—C5—C5A49.37 (18)
C4—C3—C13—C1472.43 (18)C7—C12—C11—C10−1.3 (3)
C12—C7—C8—C90.4 (2)C12—C11—C10—C90.7 (4)
C2—C7—C8—C9−178.70 (14)C8—C9—C10—C110.5 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1A···Cli0.822.393.2110 (14)176
N2—H2B···Cli0.862.213.0620 (14)171
N1—H1B···Clii0.862.253.0280 (15)150

Symmetry codes: (i) ; (ii) .

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: KP2265).

References

  • Bruker (2001). SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2005). APEX2 Bruker AXS Inc., Madison, Wisconsin, USA.
  • Rabe, P. (1904). Lieb. Ann. Bd 332, 18–22.
  • Raptis, R. G., Staples, R. J., King, C. & Fackler, J. P. (1993). Acta Cryst. C49, 1716–1719.
  • Sheldrick, G. M. (2003). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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