Homopropargyl alcohol 5,5-di­phenyl­pent-2-yne-1,5-diol

Umaña, C.A.; Pineda, L.W.; Cabezas, J.A.

doi:10.1107/S2414314618016188

organic compounds

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Volume 3| Part 11| November 2018| x181618

https://doi.org/10.1107/S2414314618016188

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Homopropargyl alcohol 5,5-diphenylpent-2-yne-1,5-diol

Christian A. Umaña,^a Leslie W. Pineda ^a,^b and Jorge A. Cabezas ^a ^*

^aEscuela de Química, Universidad de Costa Rica, 2060, San José, Costa Rica, and ^bCentro de Electroquímica y Energía Química (CELEQ), Universidad de Costa, Rica, 2060 San José, Costa Rica
^*Correspondence e-mail: jorge.cabezas@ucr.ac.cr

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 19 October 2018; accepted 15 November 2018; online 22 November 2018)

In the title compound, C₁₇H₁₆O₂, the central carbon atom has a distorted tetrahedral geometry [spread of angles = 105.71 (8)–112.75 (9)°] for its bonds to a homopropargylic but-2-yn-1-ol moiety, a hydroxy group and two phenyl substituents. In the crystal, O—H⋯O hydrogen-bonding interactions link the molecules into [001] chains and C—H⋯π(ring) contacts consolidate the packing.

Keywords: crystal structure; homopropargyl alcohols; 1,3-dilithiopropyne; propargylation; alkynes.

CCDC reference: 1858284

Structure description

Poly-functional homopropargylic alcohols are very useful intermediates in the synthesis of a variety of organic compounds (Kim et al., 2017 ; Foley & Leighton, 2015 ; Francais et al., 2010 ; Hosseyni et al., 2016 ). Their preparation usually involves multi-step synthesis (Midland et al., 1984 ). The crystal structure of 5,5-diphenyl-2-pentyn-1,5-diol is reported herein.

The crystal structure of the title compound features a distorted tetrahedral geometry for the central carbon atom (C7) for which the bonding sphere is made of a homopropargylic 2-butyn-1-ol fragment, a hydroxy group and two phenyl groups (Fig. 1). The central carbon atom has angles that deviate from the ideal value (109.4°), mainly because of the bulky phenyl groups attached to it. The dihedral angle between the rings is 80.79 (6)°. The bond length of the carbon-[carbon triple bond (C15≡C16) is 1.190 (2) Å, with the C14—C15—C16 angle being 174.11 (12)°.

Figure 1
The title molecule with 50% probability ellipsoids.

In the crystal, O—H⋯O hydrogen-bonding interactions are observed between molecules whose acceptor atoms are in a different asymmetric unit, forming a ring with an R(8) graph-set motif (Table 1 and Fig. 2) as a component of [001] chains. The packing is consolidated by C—H⋯π interactions (Table 1 and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C1–C6 and C8–C13 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.86	1.91	2.7493 (12)	164
O2—H2′⋯O1ⁱⁱ	0.86	1.87	2.7056 (12)	164
C5—H5⋯Cg2ⁱⁱⁱ	0.95	2.80	3.7122 (13)	160
C17—H17A⋯Cg1ⁱ	0.99	3.00	3.6172 (13)	122
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x, y, z-1; (iii) x+1, y, z.

Figure 2
The crystal packing of the title compound. O–H⋯O hydrogen bonds and the C–H⋯π(ring) interactions are shown, respectively, as black, green and red dashed lines.

Synthesis and crystallization

This highly substituted homopropargyl alcohol was synthesized, in a one-pot reaction, by the sequential treatment of propargyl bromide, with n-BuLi and TMEDA at −78°C, followed by reaction with benzophenone. The reaction intermediate thus obtained, was treated with paraformaldehyde overnight (Fig. 3), according to the literature procedure (Cabezas et al., 2001 ). The volatile by-product obtained (2-butyn-1-ol) was removed by Kugelrohr distillation and the residue was purified by column chromatography (ether:hexane) and the product obtained was recrystallized from a mixed ethyl ether:hexanes (1:1) solvent mixture to give colourless block-like crystals.

Figure 3
A synthetic scheme for the preparation of the title compound.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₆O₂
M_r	252.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.9772 (3), 22.8528 (8), 7.3075 (3)
β (°)	92.791 (1)
V (Å³)	1330.59 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.50 × 0.34 × 0.25

Data collection
Diffractometer	Bruker D8 Venture
Absorption correction	Multi-scan (SADABS; Bruker, 2015 )
T_min, T_max	0.727, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	65030, 3060, 2668
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.104, 1.03
No. of reflections	3060
No. of parameters	176
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.25
Computer programs: APEX3 and SAINT (Bruker, 2015), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and Mercury (Macrae et al., 2006 ).

Structural data

CCDC reference: 1858284

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314618016188/hb4268sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618016188/hb4268Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618016188/hb4268Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2015); cell refinement: APEX3 (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).

5,5-Diphenylpent-2-yne-1,5-diol top

Crystal data top

C₁₇H₁₆O₂	F(000) = 536
M_r = 252.30	D_x = 1.259 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.9772 (3) Å	Cell parameters from 117 reflections
b = 22.8528 (8) Å	θ = 3.6–23.1°
c = 7.3075 (3) Å	µ = 0.08 mm⁻¹
β = 92.791 (1)°	T = 100 K
V = 1330.59 (9) Å³	Block, colourless
Z = 4	0.50 × 0.34 × 0.25 mm

Data collection top

Bruker D8 Venture diffractometer	3060 independent reflections
Radiation source: Incoatec Microsource	2668 reflections with I > 2σ(I)
Mirrors monochromator	R_int = 0.050
Detector resolution: 10.4167 pixels mm^-1	θ_max = 27.5°, θ_min = 2.6°
ω scans	h = −8→10
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −29→29
T_min = 0.727, T_max = 0.746	l = −9→9
65030 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.053P)² + 0.6384P] where P = (F_o² + 2F_c²)/3
3060 reflections	(Δ/σ)_max = 0.001
176 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.27538 (10)	0.54181 (3)	0.43375 (11)	0.01258 (19)
H1	0.345 (2)	0.5263 (5)	0.3615 (17)	0.019*
O2	0.46943 (11)	0.51425 (4)	−0.26458 (12)	0.0171 (2)
H2'	0.4133 (13)	0.5299 (7)	−0.355 (2)	0.026*
C1	0.34385 (14)	0.63310 (5)	0.28443 (15)	0.0115 (2)
C2	0.33084 (15)	0.66221 (5)	0.11643 (17)	0.0159 (2)
H2	0.2316	0.6583	0.0402	0.019*
C3	0.46201 (17)	0.69690 (6)	0.05955 (18)	0.0206 (3)
H3	0.4515	0.7166	−0.0549	0.025*
C4	0.60738 (17)	0.70284 (5)	0.16880 (18)	0.0202 (3)
H4	0.6968	0.7264	0.1294	0.024*
C5	0.62206 (15)	0.67418 (5)	0.33639 (18)	0.0178 (3)
H5	0.722	0.678	0.4116	0.021*
C6	0.49087 (15)	0.63986 (5)	0.39436 (16)	0.0149 (2)
H6	0.5013	0.6208	0.5099	0.018*
C7	0.20382 (14)	0.59370 (5)	0.35016 (15)	0.0104 (2)
C8	0.10203 (14)	0.62267 (5)	0.49755 (15)	0.0117 (2)
C9	−0.01385 (15)	0.58905 (5)	0.58940 (17)	0.0159 (2)
H9	−0.0277	0.5488	0.5593	0.019*
C10	−0.10905 (16)	0.61360 (6)	0.72402 (17)	0.0196 (3)
H10	−0.1869	0.5902	0.7857	0.024*
C11	−0.09031 (16)	0.67244 (6)	0.76825 (17)	0.0201 (3)
H11	−0.1553	0.6893	0.8601	0.024*
C12	0.02357 (16)	0.70637 (6)	0.67798 (17)	0.0192 (3)
H12	0.0364	0.7466	0.7079	0.023*
C13	0.11950 (15)	0.68163 (5)	0.54327 (16)	0.0150 (2)
H13	0.1974	0.7052	0.4822	0.018*
C14	0.08274 (14)	0.57347 (5)	0.19017 (15)	0.0127 (2)
H14A	−0.0068	0.5488	0.2391	0.015*
H14B	0.0291	0.6081	0.1309	0.015*
C15	0.17153 (14)	0.54009 (5)	0.05346 (16)	0.0127 (2)
C16	0.25424 (14)	0.51196 (5)	−0.04534 (16)	0.0138 (2)
C17	0.36115 (15)	0.47781 (5)	−0.16380 (16)	0.0153 (2)
H17A	0.43	0.4502	−0.0875	0.018*
H17B	0.2892	0.4545	−0.2507	0.018*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0132 (4)	0.0123 (4)	0.0125 (4)	0.0038 (3)	0.0025 (3)	0.0022 (3)
O2	0.0142 (4)	0.0248 (5)	0.0124 (4)	0.0041 (3)	0.0021 (3)	0.0033 (3)
C1	0.0112 (5)	0.0105 (5)	0.0130 (5)	0.0007 (4)	0.0032 (4)	−0.0014 (4)
C2	0.0163 (6)	0.0165 (5)	0.0149 (6)	−0.0008 (4)	0.0010 (4)	0.0016 (4)
C3	0.0261 (7)	0.0181 (6)	0.0183 (6)	−0.0035 (5)	0.0070 (5)	0.0029 (5)
C4	0.0191 (6)	0.0173 (6)	0.0252 (7)	−0.0058 (5)	0.0109 (5)	−0.0044 (5)
C5	0.0122 (5)	0.0179 (6)	0.0234 (6)	−0.0019 (4)	0.0021 (5)	−0.0071 (5)
C6	0.0147 (5)	0.0148 (5)	0.0152 (6)	0.0004 (4)	0.0006 (4)	−0.0018 (4)
C7	0.0101 (5)	0.0108 (5)	0.0102 (5)	0.0009 (4)	0.0008 (4)	0.0013 (4)
C8	0.0107 (5)	0.0150 (5)	0.0095 (5)	0.0031 (4)	−0.0004 (4)	0.0004 (4)
C9	0.0174 (6)	0.0148 (5)	0.0160 (6)	0.0029 (4)	0.0043 (4)	0.0030 (4)
C10	0.0201 (6)	0.0240 (6)	0.0154 (6)	0.0057 (5)	0.0067 (5)	0.0054 (5)
C11	0.0211 (6)	0.0272 (6)	0.0122 (5)	0.0094 (5)	0.0034 (5)	−0.0015 (5)
C12	0.0212 (6)	0.0183 (6)	0.0180 (6)	0.0042 (5)	−0.0004 (5)	−0.0057 (5)
C13	0.0139 (5)	0.0160 (5)	0.0151 (6)	0.0010 (4)	0.0005 (4)	−0.0014 (4)
C14	0.0103 (5)	0.0156 (5)	0.0122 (5)	−0.0006 (4)	0.0009 (4)	−0.0013 (4)
C15	0.0108 (5)	0.0153 (5)	0.0118 (5)	−0.0017 (4)	−0.0016 (4)	0.0000 (4)
C16	0.0116 (5)	0.0170 (5)	0.0126 (5)	−0.0015 (4)	−0.0015 (4)	−0.0002 (4)
C17	0.0134 (5)	0.0173 (5)	0.0151 (6)	0.0006 (4)	0.0009 (4)	−0.0029 (4)

Geometric parameters (Å, º) top

O1—C7	1.4391 (13)	C8—C13	1.3936 (16)
O1—H1	0.860 (17)	C8—C9	1.3985 (16)
O2—C17	1.4296 (14)	C9—C10	1.3900 (16)
O2—H2'	0.857 (18)	C9—H9	0.95
C1—C2	1.3957 (16)	C10—C11	1.3892 (19)
C1—C6	1.3974 (16)	C10—H10	0.95
C1—C7	1.5302 (15)	C11—C12	1.3856 (19)
C2—C3	1.3923 (17)	C11—H11	0.95
C2—H2	0.95	C12—C13	1.3956 (16)
C3—C4	1.3822 (19)	C12—H12	0.95
C3—H3	0.95	C13—H13	0.95
C4—C5	1.3888 (19)	C14—C15	1.4665 (15)
C4—H4	0.95	C14—H14A	0.99
C5—C6	1.3903 (16)	C14—H14B	0.99
C5—H5	0.95	C15—C16	1.1900 (17)
C6—H6	0.95	C16—C17	1.4690 (16)
C7—C8	1.5307 (15)	C17—H17A	0.99
C7—C14	1.5503 (15)	C17—H17B	0.99

C7—O1—H1	109.5	C10—C9—C8	120.97 (11)
C17—O2—H2'	109.5	C10—C9—H9	119.5
C2—C1—C6	118.51 (11)	C8—C9—H9	119.5
C2—C1—C7	122.17 (10)	C11—C10—C9	119.94 (12)
C6—C1—C7	119.32 (10)	C11—C10—H10	120.0
C3—C2—C1	120.61 (12)	C9—C10—H10	120.0
C3—C2—H2	119.7	C12—C11—C10	119.77 (11)
C1—C2—H2	119.7	C12—C11—H11	120.1
C4—C3—C2	120.34 (12)	C10—C11—H11	120.1
C4—C3—H3	119.8	C11—C12—C13	120.25 (11)
C2—C3—H3	119.8	C11—C12—H12	119.9
C3—C4—C5	119.69 (11)	C13—C12—H12	119.9
C3—C4—H4	120.2	C8—C13—C12	120.59 (11)
C5—C4—H4	120.2	C8—C13—H13	119.7
C4—C5—C6	120.15 (12)	C12—C13—H13	119.7
C4—C5—H5	119.9	C15—C14—C7	111.41 (9)
C6—C5—H5	119.9	C15—C14—H14A	109.3
C5—C6—C1	120.69 (11)	C7—C14—H14A	109.3
C5—C6—H6	119.7	C15—C14—H14B	109.3
C1—C6—H6	119.7	C7—C14—H14B	109.3
O1—C7—C1	109.72 (9)	H14A—C14—H14B	108.0
O1—C7—C8	105.71 (8)	C16—C15—C14	174.11 (12)
C1—C7—C8	112.75 (9)	C15—C16—C17	178.17 (13)
O1—C7—C14	107.11 (9)	O2—C17—C16	112.13 (10)
C1—C7—C14	112.10 (9)	O2—C17—H17A	109.2
C8—C7—C14	109.10 (9)	C16—C17—H17A	109.2
C13—C8—C9	118.48 (11)	O2—C17—H17B	109.2
C13—C8—C7	122.46 (10)	C16—C17—H17B	109.2
C9—C8—C7	119.06 (10)	H17A—C17—H17B	107.9

C6—C1—C2—C3	0.37 (17)	C14—C7—C8—C13	−115.62 (12)
C7—C1—C2—C3	−178.85 (11)	O1—C7—C8—C9	−50.95 (13)
C1—C2—C3—C4	0.18 (19)	C1—C7—C8—C9	−170.83 (10)
C2—C3—C4—C5	−0.24 (19)	C14—C7—C8—C9	63.93 (13)
C3—C4—C5—C6	−0.26 (18)	C13—C8—C9—C10	−0.35 (18)
C4—C5—C6—C1	0.83 (18)	C7—C8—C9—C10	−179.92 (11)
C2—C1—C6—C5	−0.88 (17)	C8—C9—C10—C11	0.34 (19)
C7—C1—C6—C5	178.37 (10)	C9—C10—C11—C12	−0.10 (19)
C2—C1—C7—O1	138.56 (11)	C10—C11—C12—C13	−0.11 (19)
C6—C1—C7—O1	−40.66 (13)	C9—C8—C13—C12	0.13 (17)
C2—C1—C7—C8	−103.91 (12)	C7—C8—C13—C12	179.69 (10)
C6—C1—C7—C8	76.87 (13)	C11—C12—C13—C8	0.09 (18)
C2—C1—C7—C14	19.69 (14)	O1—C7—C14—C15	−60.24 (11)
C6—C1—C7—C14	−159.53 (10)	C1—C7—C14—C15	60.16 (12)
O1—C7—C8—C13	129.49 (11)	C8—C7—C14—C15	−174.22 (9)
C1—C7—C8—C13	9.62 (15)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C1–C6 and C8–C13 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.86	1.91	2.7493 (12)	164
O2—H2′···O1ⁱⁱ	0.86	1.87	2.7056 (12)	164
C5—H5···Cg2ⁱⁱⁱ	0.95	2.80	3.7122 (13)	160
C17—H17A···Cg1ⁱ	0.99	3.00	3.6172 (13)	122

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

Funding information

We thank the Sistema de Estudios de Posgrado (SEP), Universidad de Costa Rica (UCR) for a stipend to CAU, and the Vicerrectoría de Investigación (UCR) for financial support.

References

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Cabezas, J. A., Pereira, A. & Amey, A. (2001). Tetrahedron Lett. 42, 6819–6822. CrossRef Google Scholar
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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Homopropargyl alcohol 5,5-di­phenyl­pent-2-yne-1,5-diol

Structure description

Synthesis and crystallization

Refinement

Structural data

Funding information

References

organic compounds

Homopropargyl alcohol 5,5-diphenylpent-2-yne-1,5-diol