Crystal structure of 1,4,5,6,7,8,9,10,11,12,13-undeca­hydro­cyclo­dodeca[c]pyrazol-3-ol

Casey C Raymond; Michael A Knopp

doi:10.1107/S2056989015016746

. 2015 Sep 12;71(Pt 10):o752–o753. doi: 10.1107/S2056989015016746

Crystal structure of 1,4,5,6,7,8,9,10,11,12,13-undecahydrocyclododeca[c]pyrazol-3-ol

Casey C Raymond ^a,^*, Michael A Knopp ^b

PMCID: PMC4647396 PMID: 26594458

Abstract

The title compound, C₁₃H₂₂N₂O, crystallized as a pyrazolol tautomer. The 12-membered macrocycle has a distorted chair conformation. In the crystal, molecules are linked via pairs of O—H⋯N hydrogen bonds, forming inversion dimers. The dimers are linked via N—H⋯π and C—H⋯π interactions, forming slabs parallel to the bc plane.

Keywords: crystal structure, pyrazolol, tautomer, pyrazolone, macrocycle, O—H⋯N hydrogen bond, N—H⋯π interaction

Related literature

The crystal structure of the title compound clarifies the connectivity of a class of pyrazolone-derived materials, specifically revealing a pyrazolol tautomer instead of the expected pyrazolone. For the synthesis of the title compound, see: Silveira et al. (1977 ▸). For the structure of a similar tautomer, see: Silveira et al. (1980 ▸). For a review of the chemistry of pyrazolones, pyrazolidones and their derivatives, see: Wiley & Wiley (1964 ▸).

Experimental

Crystal data

C₁₃H₂₂N₂O
M _r = 222.32
Monoclinic,
a = 30.008 (2) Å
b = 7.4764 (5) Å
c = 11.6516 (8) Å
β = 105.4374 (12)°
V = 2519.7 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.59 × 0.33 × 0.11 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▸) T _min = 0.871, T _max = 0.992
14420 measured reflections
3845 independent reflections
3383 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.119
S = 1.03
3845 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▸); cell refinement: SAINT (Bruker, 2007 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015016746/su5204sup1.cif

e-71-0o752-sup1.cif^{(446KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015016746/su5204Isup2.hkl

e-71-0o752-Isup2.hkl^{(307KB, hkl)}

Click here for additional data file.^{(2.5KB, cdx)}

Supporting information file. DOI: 10.1107/S2056989015016746/su5204Isup3.cdx

Click here for additional data file.^{(2.3KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015016746/su5204Isup4.cml

Click here for additional data file.^{(1.7MB, tif)}

. DOI: 10.1107/S2056989015016746/su5204fig1.tif

A view of the molecular structure of the title compound, with atom labeling. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.^{(1.3MB, tif)}

b . DOI: 10.1107/S2056989015016746/su5204fig2.tif

A view along the b axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1), and C-bound H atoms have been omitted for clarity.

CCDC reference: 1422925

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

Cg is the centroid of the pyrazol ring N1/N2/C1C3.

DHA	DH	HA	D A	DHA
O1H1N1ⁱ	0.84	1.87	2.7072(12)	177
N2H2Cg ⁱⁱ	0.88	2.58	3.4429(11)	166
C6H6B Cg ⁱⁱⁱ	0.99	2.71	3.5734(13)	147

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors thank M. Zeller and Youngstown State University for the X-ray data collection.

supplementary crystallographic information

S1. Comment

The crystal structure of the title compound, Fig. 1, clarifies the connectivity of a class of pyrazolone-derived materials, specifically revealing a pyrzazolol tautomer instead of the expected pyrazolone. The bond lengths and angles support this pyrazolol tautomer in the solid state. The crystal structure reveals a different isomer than originally proposed by by (Silveira et al., 1977). However, it is similar to a tautomer proposed in a subsequent investigation (Silveira et al., 1980).

Specifically, we have determined that the compound of interest contains an alcohol group instead of the postulated ketone. The alcoholic group is also consistent with a positive reaction with iron(III) solutions, yielding a dark purple color (Wiley & Wiley, 1964).

In the crystal, molecules are linked via a pair of O—H···N hydrogen bonds forming inversion dimers (Fig. 2 and Table 1). The dimers are linked via N—H···π and C—H···π interactions forming slabs parallel to the bc plane (Table 1).

S2. Synthesis and crystallization

The title compound was prepared as described by (Silveira et al., 1977). Colorless crystals were obtained by recrystallization by slow cooling of a saturated, warm ethanol solution.

S3. Refinement details

The NH and OH H atoms were located in a difference Fourier map. All of the H atoms were placed in calculated positions and refined as riding: O—H = 0.84 Å, N—H = 0.88 Å, C—H = 0.99 Å with U_iso(H) = 1.5U_eq(O) for the OH H atom and 1.2U_eq(N,C) for other H atoms.