organic compounds
c]pyrazol-3-ol
of 1,4,5,6,7,8,9,10,11,12,13-undecahydrocyclododeca[aDepartment of Chemistry, 296 Shineman Center, SUNY Oswego, Oswego, NY 13126, USA, and bEnvironmental Science and Sustainability Department, 307 South Hall, 181 Main St., University of Maine at Presque Isle, Presque Isle, Maine 04769, USA
*Correspondence e-mail: casey.raymond@oswego.edu
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.
CCDC reference: 1422925
1. Related literature
The 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).
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: Silveira2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: APEX2 (Bruker, 2007); cell 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).
Supporting information
CCDC reference: 1422925
10.1107/S2056989015016746/su5204sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015016746/su5204Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015016746/su5204Isup3.cdx
Supporting information file. DOI: 10.1107/S2056989015016746/su5204Isup4.cml
The
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 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).
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.
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).Fig. 1. A view of the molecular structure of the title compound, with atom labeling. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. 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. |
C13H22N2O | F(000) = 976 |
Mr = 222.32 | Dx = 1.172 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 30.008 (2) Å | Cell parameters from 9304 reflections |
b = 7.4764 (5) Å | θ = 2.8–30.5° |
c = 11.6516 (8) Å | µ = 0.08 mm−1 |
β = 105.4374 (12)° | T = 100 K |
V = 2519.7 (3) Å3 | Plate, colorless |
Z = 8 | 0.59 × 0.33 × 0.11 mm |
Bruker APEX CCD diffractometer | 3383 reflections with I > 2σ(I) |
ω and phi scans | Rint = 0.041 |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | θmax = 30.5°, θmin = 2.8° |
Tmin = 0.871, Tmax = 0.992 | h = −42→42 |
14420 measured reflections | k = −10→10 |
3845 independent reflections | l = −16→16 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.051 | H-atom parameters constrained |
wR(F2) = 0.119 | w = 1/[σ2(Fo2) + (0.0437P)2 + 2.2017P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
3845 reflections | Δρmax = 0.41 e Å−3 |
146 parameters | Δρmin = −0.20 e Å−3 |
C13H22N2O | V = 2519.7 (3) Å3 |
Mr = 222.32 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 30.008 (2) Å | µ = 0.08 mm−1 |
b = 7.4764 (5) Å | T = 100 K |
c = 11.6516 (8) Å | 0.59 × 0.33 × 0.11 mm |
β = 105.4374 (12)° |
Bruker APEX CCD diffractometer | 3845 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | 3383 reflections with I > 2σ(I) |
Tmin = 0.871, Tmax = 0.992 | Rint = 0.041 |
14420 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.41 e Å−3 |
3845 reflections | Δρmin = −0.20 e Å−3 |
146 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.29213 (3) | 0.05291 (11) | 0.56411 (7) | 0.02556 (18) | |
H1 | 0.2743 | 0.0908 | 0.5005 | 0.038* | |
N1 | 0.26539 (3) | 0.31282 (13) | 0.63710 (8) | 0.0237 (2) | |
N2 | 0.27474 (3) | 0.38692 (13) | 0.74851 (8) | 0.0249 (2) | |
H2 | 0.2628 | 0.4887 | 0.7641 | 0.030* | |
C1 | 0.29108 (4) | 0.16479 (14) | 0.65347 (9) | 0.0214 (2) | |
C2 | 0.31597 (4) | 0.13945 (14) | 0.77385 (9) | 0.0208 (2) | |
C3 | 0.30426 (4) | 0.28695 (15) | 0.83204 (9) | 0.0221 (2) | |
C4 | 0.32060 (4) | 0.34607 (15) | 0.95885 (9) | 0.0240 (2) | |
H4A | 0.3412 | 0.2533 | 1.0056 | 0.029* | |
H4B | 0.2937 | 0.3591 | 0.9922 | 0.029* | |
C5 | 0.34679 (4) | 0.52462 (15) | 0.97093 (10) | 0.0258 (2) | |
H5A | 0.3241 | 0.6224 | 0.9444 | 0.031* | |
H5B | 0.3674 | 0.5230 | 0.9171 | 0.031* | |
C6 | 0.37587 (4) | 0.56546 (16) | 1.09762 (10) | 0.0284 (2) | |
H6A | 0.3889 | 0.6874 | 1.0991 | 0.034* | |
H6B | 0.3554 | 0.5647 | 1.1517 | 0.034* | |
C7 | 0.41558 (4) | 0.43390 (17) | 1.14525 (10) | 0.0296 (2) | |
H7A | 0.4026 | 0.3117 | 1.1419 | 0.036* | |
H7B | 0.4302 | 0.4623 | 1.2299 | 0.036* | |
C8 | 0.45307 (4) | 0.43498 (18) | 1.07776 (12) | 0.0336 (3) | |
H8A | 0.4392 | 0.4770 | 0.9954 | 0.040* | |
H8B | 0.4774 | 0.5215 | 1.1165 | 0.040* | |
C9 | 0.47548 (4) | 0.2527 (2) | 1.07272 (12) | 0.0363 (3) | |
H9A | 0.4882 | 0.2088 | 1.1551 | 0.044* | |
H9B | 0.5017 | 0.2682 | 1.0370 | 0.044* | |
C10 | 0.44297 (4) | 0.10995 (17) | 1.00175 (10) | 0.0291 (2) | |
H10A | 0.4592 | −0.0065 | 1.0134 | 0.035* | |
H10B | 0.4159 | 0.0992 | 1.0346 | 0.035* | |
C11 | 0.42583 (4) | 0.14687 (16) | 0.86845 (10) | 0.0263 (2) | |
H11A | 0.4529 | 0.1628 | 0.8359 | 0.032* | |
H11B | 0.4082 | 0.2603 | 0.8563 | 0.032* | |
C12 | 0.39528 (4) | −0.00152 (16) | 0.79927 (10) | 0.0266 (2) | |
H12A | 0.4114 | −0.1172 | 0.8203 | 0.032* | |
H12B | 0.3913 | 0.0185 | 0.7131 | 0.032* | |
C13 | 0.34726 (4) | −0.01540 (15) | 0.82185 (10) | 0.0248 (2) | |
H13A | 0.3323 | −0.1270 | 0.7850 | 0.030* | |
H13B | 0.3511 | −0.0241 | 0.9087 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0306 (4) | 0.0225 (4) | 0.0221 (4) | 0.0039 (3) | 0.0044 (3) | −0.0037 (3) |
N1 | 0.0235 (4) | 0.0246 (5) | 0.0222 (4) | 0.0022 (3) | 0.0048 (3) | −0.0047 (3) |
N2 | 0.0259 (4) | 0.0248 (5) | 0.0227 (4) | 0.0054 (4) | 0.0044 (3) | −0.0055 (4) |
C1 | 0.0209 (4) | 0.0205 (5) | 0.0238 (5) | −0.0019 (4) | 0.0076 (4) | −0.0018 (4) |
C2 | 0.0222 (4) | 0.0189 (5) | 0.0219 (5) | −0.0015 (4) | 0.0069 (4) | 0.0006 (4) |
C3 | 0.0210 (4) | 0.0230 (5) | 0.0225 (5) | −0.0004 (4) | 0.0059 (4) | −0.0001 (4) |
C4 | 0.0286 (5) | 0.0230 (5) | 0.0207 (5) | 0.0016 (4) | 0.0069 (4) | −0.0010 (4) |
C5 | 0.0313 (5) | 0.0210 (5) | 0.0227 (5) | 0.0025 (4) | 0.0028 (4) | −0.0006 (4) |
C6 | 0.0342 (6) | 0.0238 (5) | 0.0242 (5) | 0.0046 (4) | 0.0023 (4) | −0.0052 (4) |
C7 | 0.0342 (6) | 0.0298 (6) | 0.0220 (5) | 0.0067 (5) | 0.0026 (4) | −0.0025 (4) |
C8 | 0.0302 (6) | 0.0344 (7) | 0.0338 (6) | −0.0005 (5) | 0.0045 (5) | −0.0064 (5) |
C9 | 0.0291 (6) | 0.0442 (8) | 0.0317 (6) | 0.0084 (5) | 0.0013 (5) | −0.0069 (5) |
C10 | 0.0312 (6) | 0.0311 (6) | 0.0236 (5) | 0.0100 (5) | 0.0050 (4) | −0.0001 (4) |
C11 | 0.0258 (5) | 0.0301 (6) | 0.0238 (5) | 0.0033 (4) | 0.0080 (4) | 0.0005 (4) |
C12 | 0.0311 (5) | 0.0260 (5) | 0.0229 (5) | 0.0076 (4) | 0.0076 (4) | −0.0010 (4) |
C13 | 0.0312 (5) | 0.0176 (5) | 0.0254 (5) | 0.0011 (4) | 0.0072 (4) | 0.0015 (4) |
O1—C1 | 1.3424 (13) | C7—H7A | 0.9900 |
O1—H1 | 0.8400 | C7—H7B | 0.9900 |
N1—C1 | 1.3331 (14) | C8—C9 | 1.5280 (19) |
N1—N2 | 1.3700 (12) | C8—H8A | 0.9900 |
N2—C3 | 1.3533 (14) | C8—H8B | 0.9900 |
N2—H2 | 0.8800 | C9—C10 | 1.5312 (18) |
C1—C2 | 1.4153 (14) | C9—H9A | 0.9900 |
C2—C3 | 1.3879 (15) | C9—H9B | 0.9900 |
C2—C13 | 1.5018 (15) | C10—C11 | 1.5257 (16) |
C3—C4 | 1.4944 (15) | C10—H10A | 0.9900 |
C4—C5 | 1.5364 (16) | C10—H10B | 0.9900 |
C4—H4A | 0.9900 | C11—C12 | 1.5257 (17) |
C4—H4B | 0.9900 | C11—H11A | 0.9900 |
C5—C6 | 1.5322 (16) | C11—H11B | 0.9900 |
C5—H5A | 0.9900 | C12—C13 | 1.5355 (16) |
C5—H5B | 0.9900 | C12—H12A | 0.9900 |
C6—C7 | 1.5309 (16) | C12—H12B | 0.9900 |
C6—H6A | 0.9900 | C13—H13A | 0.9900 |
C6—H6B | 0.9900 | C13—H13B | 0.9900 |
C7—C8 | 1.5345 (18) | ||
C1—O1—H1 | 109.5 | H7A—C7—H7B | 107.6 |
C1—N1—N2 | 103.62 (9) | C9—C8—C7 | 113.91 (12) |
C3—N2—N1 | 112.81 (9) | C9—C8—H8A | 108.8 |
C3—N2—H2 | 123.6 | C7—C8—H8A | 108.8 |
N1—N2—H2 | 123.6 | C9—C8—H8B | 108.8 |
N1—C1—O1 | 122.57 (10) | C7—C8—H8B | 108.8 |
N1—C1—C2 | 112.67 (9) | H8A—C8—H8B | 107.7 |
O1—C1—C2 | 124.76 (10) | C8—C9—C10 | 114.75 (10) |
C3—C2—C1 | 104.02 (9) | C8—C9—H9A | 108.6 |
C3—C2—C13 | 130.18 (10) | C10—C9—H9A | 108.6 |
C1—C2—C13 | 125.80 (10) | C8—C9—H9B | 108.6 |
N2—C3—C2 | 106.85 (9) | C10—C9—H9B | 108.6 |
N2—C3—C4 | 121.83 (10) | H9A—C9—H9B | 107.6 |
C2—C3—C4 | 131.22 (10) | C11—C10—C9 | 114.67 (11) |
C3—C4—C5 | 111.89 (9) | C11—C10—H10A | 108.6 |
C3—C4—H4A | 109.2 | C9—C10—H10A | 108.6 |
C5—C4—H4A | 109.2 | C11—C10—H10B | 108.6 |
C3—C4—H4B | 109.2 | C9—C10—H10B | 108.6 |
C5—C4—H4B | 109.2 | H10A—C10—H10B | 107.6 |
H4A—C4—H4B | 107.9 | C10—C11—C12 | 113.49 (10) |
C4—C5—C6 | 114.06 (10) | C10—C11—H11A | 108.9 |
C4—C5—H5A | 108.7 | C12—C11—H11A | 108.9 |
C6—C5—H5A | 108.7 | C10—C11—H11B | 108.9 |
C4—C5—H5B | 108.7 | C12—C11—H11B | 108.9 |
C6—C5—H5B | 108.7 | H11A—C11—H11B | 107.7 |
H5A—C5—H5B | 107.6 | C11—C12—C13 | 114.71 (9) |
C7—C6—C5 | 114.20 (9) | C11—C12—H12A | 108.6 |
C7—C6—H6A | 108.7 | C13—C12—H12A | 108.6 |
C5—C6—H6A | 108.7 | C11—C12—H12B | 108.6 |
C7—C6—H6B | 108.7 | C13—C12—H12B | 108.6 |
C5—C6—H6B | 108.7 | H12A—C12—H12B | 107.6 |
H6A—C6—H6B | 107.6 | C2—C13—C12 | 113.98 (9) |
C6—C7—C8 | 114.64 (10) | C2—C13—H13A | 108.8 |
C6—C7—H7A | 108.6 | C12—C13—H13A | 108.8 |
C8—C7—H7A | 108.6 | C2—C13—H13B | 108.8 |
C6—C7—H7B | 108.6 | C12—C13—H13B | 108.8 |
C8—C7—H7B | 108.6 | H13A—C13—H13B | 107.7 |
C1—N1—N2—C3 | −1.49 (12) | N2—C3—C4—C5 | −60.38 (14) |
N2—N1—C1—O1 | −179.34 (10) | C2—C3—C4—C5 | 115.43 (13) |
N2—N1—C1—C2 | 1.48 (12) | C3—C4—C5—C6 | −163.47 (10) |
N1—C1—C2—C3 | −0.97 (12) | C4—C5—C6—C7 | 64.21 (14) |
O1—C1—C2—C3 | 179.87 (10) | C5—C6—C7—C8 | 64.54 (14) |
N1—C1—C2—C13 | 178.86 (10) | C6—C7—C8—C9 | −147.20 (11) |
O1—C1—C2—C13 | −0.30 (17) | C7—C8—C9—C10 | 65.43 (15) |
N1—N2—C3—C2 | 0.93 (13) | C8—C9—C10—C11 | 66.47 (15) |
N1—N2—C3—C4 | 177.64 (10) | C9—C10—C11—C12 | 177.39 (10) |
C1—C2—C3—N2 | 0.01 (11) | C10—C11—C12—C13 | 70.67 (12) |
C13—C2—C3—N2 | −179.81 (10) | C3—C2—C13—C12 | −101.48 (13) |
C1—C2—C3—C4 | −176.27 (11) | C1—C2—C13—C12 | 78.73 (13) |
C13—C2—C3—C4 | 3.91 (19) | C11—C12—C13—C2 | 68.41 (13) |
Cg is the centroid of the pyrazol ring N1/N2/C1–C3. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1i | 0.84 | 1.87 | 2.7072 (12) | 177 |
N2—H2···Cgii | 0.88 | 2.58 | 3.4429 (11) | 166 |
C6—H6B···Cgiii | 0.99 | 2.71 | 3.5734 (13) | 147 |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1/2, y+1/2, −z+3/2; (iii) x, −y+1, z+1/2. |
Cg is the centroid of the pyrazol ring N1/N2/C1–C3. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1i | 0.84 | 1.87 | 2.7072 (12) | 177 |
N2—H2···Cgii | 0.88 | 2.58 | 3.4429 (11) | 166 |
C6—H6B···Cgiii | 0.99 | 2.71 | 3.5734 (13) | 147 |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1/2, y+1/2, −z+3/2; (iii) x, −y+1, z+1/2. |
Acknowledgements
The authors thank M. Zeller and Youngstown State University for the X-ray data collection.
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