Homopropargyl alcohol 1,1-di­phenyl­but-3-yn-1-ol

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

doi:10.1107/S241431461801619X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 11| November 2018| x181619

https://doi.org/10.1107/S241431461801619X

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Homopropargyl alcohol 1,1-diphenylbut-3-yn-1-ol

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)

The asymmetric unit of the title compound, C₁₆H₁₄O, contains one molecule with a central carbon atom having a distorted tetrahedral geometry made of a propargylic fragment, a hydroxy group and two aromatic rings. Directional interactions such as unusual O—H⋯π contacts are observed between the molecules in the crystal.

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

CCDC reference: 1858285

Structure description

Homopropargylic alcohols are very useful intermediates in the synthesis of a variety of organic compounds of natural (Kim et al., 2017 ; Foley & Leighton, 2015 ; Francais et al., 2010 ) and synthetic origin (Hosseyni et al., 2016 ; Gao et al., 2014 ; Trost & Rhee, 2003 ; Nicolaou et al., 1990 ; Yadav & Maiti, 2002 ). The crystal structure of homopropargyl alcohol 1,1-diphenylbut-3-yn-1-ol is presented herein.

The crystal structure of the title compound comprises a central carbon atom (C7) tetrahedrally bonded to a propargylic moiety, a hydroxy functional group and two phenyl rings (Fig. 1). The bond angles at C7 deviate from the ideal value (109.5°) with angles ranging from 106.13 (11) to 112.06 (11)°, mainly because of the bulky substituent groups attached to this atom. The bond length of the terminal carbon–carbon triple bond (C15≡C16) is 1.190 (2) Å; the propargylic unit (C14–C15–C16) exhibits an angle of 176.26 (15)°, slightly distorted from the linear geometry expected (180°).

Figure 1
The title molecule with 50% probability ellipsoids.

In the crystal, the title compound features uncommon O—H⋯π interactions with bond lengths for atom H1 and the C4 and C5 aromatic carbon atoms of 2.72 and 2.80 Å, respectively (symmetry operation 1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z) (Fig. 2). Moreover, the hydrogen atom (H16) of the terminal alkyne group has short contacts with carbon atoms of the aromatic ring C9 (2.79 Å) and C10 (2.68 Å), with corresponding symmetry operation −1 + x, y, z. Carbon atom C15 of the alkyne fragment accepts an interaction from hydrogen atom H9 bound to aromatic carbon C9 (2.85 Å); symmetry operation $[{1\over 2}]$ + x, $[{1\over 2}]$ − y,1 − z.

Figure 2
Packing view of the title compound. O–H⋯π, terminal alkyne hydrogen atom⋯π and terminal alkyne carbon atom with aromatic hydrogen atom contacts are shown, respectively, as red, blue and green dashed lines.

Synthesis and crystallization

The title compound was synthesized by treatment of propargyl bromide with n-BuLi and TMEDA, at −78°C, followed by addition of benzophenone (Fig. 3), according to a previously reported procedure (Cabezas et al., 2001 ). It was purified by recrystallization from an ethyl ether:hexanes (1:1) solvent mixture to afford colourless block-shaped 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 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₁₆H₁₄O
M_r	222.27
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	7.485 (5), 9.173 (7), 16.995 (13)
V (Å³)	1166.9 (15)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.40 × 0.40 × 0.35

Data collection
Diffractometer	Bruker D8 Venture
Absorption correction	Multi-scan (SADABS; Bruker, 2015 )
T_min, T_max	0.701, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	57886, 2688, 2662
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.075, 1.06
No. of reflections	2688
No. of parameters	157
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.15
Absolute structure	Flack x determined using 1109 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.06 (16)
Computer programs: APEX3 and SAINT (Bruker, 2015), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and Mercury (Macrae et al., 2006 ).

Structural data

CCDC reference: 1858285

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S241431461801619X/hb4269sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461801619X/hb4269Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431461801619X/hb4269Isup3.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).

1,1-Diphenylbut-3-yn-1-ol top

Crystal data top

C₁₆H₁₄O	D_x = 1.265 Mg m⁻³
M_r = 222.27	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 115 reflections
a = 7.485 (5) Å	θ = 3.2–24.4°
b = 9.173 (7) Å	µ = 0.08 mm⁻¹
c = 16.995 (13) Å	T = 100 K
V = 1166.9 (15) Å³	Block, colourless
Z = 4	0.40 × 0.40 × 0.35 mm
F(000) = 472

Data collection top

Bruker D8 Venture diffractometer	2688 independent reflections
Radiation source: Incoatec Microsource	2662 reflections with I > 2σ(I)
Mirrors monochromator	R_int = 0.020
Detector resolution: 10.4167 pixels mm^-1	θ_max = 27.6°, θ_min = 2.5°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −11→11
T_min = 0.701, T_max = 0.746	l = −20→22
57886 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.027	w = 1/[σ²(F_o²) + (0.0443P)² + 0.2544P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.075	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.26 e Å⁻³
2688 reflections	Δρ_min = −0.15 e Å⁻³
157 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015b)
0 restraints	Extinction coefficient: 0.038 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack x determined using 1109 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.06 (16)

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	0.57457 (13)	0.42888 (11)	0.27540 (5)	0.0168 (2)
H1	0.664 (3)	0.481 (2)	0.2894 (4)	0.025*
C1	0.32959 (17)	0.28343 (14)	0.31357 (8)	0.0126 (3)
C2	0.24610 (18)	0.17965 (14)	0.36076 (8)	0.0153 (3)
H2	0.2889	0.1624	0.4126	0.018*
C3	0.10087 (19)	0.10126 (15)	0.33270 (8)	0.0164 (3)
H3	0.0453	0.0305	0.3654	0.02*
C4	0.03638 (18)	0.12534 (15)	0.25746 (9)	0.0173 (3)
H4	−0.0627	0.0712	0.2383	0.021*
C5	0.1179 (2)	0.22922 (16)	0.21040 (8)	0.0183 (3)
H5	0.0738	0.247	0.1589	0.022*
C6	0.26348 (19)	0.30746 (14)	0.23819 (8)	0.0154 (3)
H6	0.3186	0.3782	0.2054	0.018*
C7	0.48752 (18)	0.37335 (14)	0.34344 (7)	0.0122 (3)
C8	0.41558 (17)	0.49758 (14)	0.39480 (8)	0.0121 (3)
C9	0.37060 (18)	0.47642 (15)	0.47354 (8)	0.0151 (3)
H9	0.3922	0.3846	0.4976	0.018*
C10	0.29437 (19)	0.58841 (16)	0.51711 (8)	0.0188 (3)
H10	0.2627	0.5721	0.5705	0.023*
C11	0.2641 (2)	0.72385 (16)	0.48333 (9)	0.0210 (3)
H11	0.2119	0.8002	0.5133	0.025*
C12	0.3107 (2)	0.74623 (16)	0.40560 (9)	0.0219 (3)
H12	0.2921	0.8391	0.3822	0.026*
C13	0.38473 (19)	0.63376 (16)	0.36129 (8)	0.0166 (3)
H13	0.4145	0.6501	0.3077	0.02*
C14	0.62155 (18)	0.27596 (15)	0.38847 (8)	0.0159 (3)
H14A	0.5632	0.2354	0.4359	0.019*
H14B	0.6585	0.1935	0.3546	0.019*
C15	0.77909 (19)	0.35999 (16)	0.41165 (8)	0.0170 (3)
C16	0.90564 (19)	0.43325 (17)	0.42685 (9)	0.0214 (3)
H16	1.0067	0.4917	0.439	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0153 (4)	0.0212 (5)	0.0138 (4)	−0.0062 (4)	0.0024 (4)	0.0000 (4)
C1	0.0115 (6)	0.0112 (6)	0.0151 (6)	0.0008 (5)	0.0008 (5)	−0.0032 (5)
C2	0.0157 (6)	0.0161 (6)	0.0140 (6)	−0.0008 (5)	0.0010 (5)	−0.0011 (5)
C3	0.0155 (6)	0.0148 (6)	0.0189 (6)	−0.0023 (5)	0.0038 (5)	−0.0005 (5)
C4	0.0133 (6)	0.0155 (6)	0.0231 (7)	−0.0011 (5)	−0.0010 (5)	−0.0035 (5)
C5	0.0179 (6)	0.0194 (6)	0.0176 (6)	0.0003 (5)	−0.0043 (5)	0.0001 (5)
C6	0.0162 (6)	0.0136 (6)	0.0165 (6)	−0.0006 (5)	0.0000 (5)	0.0013 (5)
C7	0.0120 (6)	0.0129 (6)	0.0117 (6)	−0.0002 (5)	0.0006 (4)	0.0005 (4)
C8	0.0090 (5)	0.0129 (6)	0.0145 (6)	−0.0010 (4)	−0.0016 (4)	−0.0016 (5)
C9	0.0145 (6)	0.0153 (6)	0.0155 (6)	−0.0021 (5)	−0.0015 (5)	−0.0005 (5)
C10	0.0157 (6)	0.0248 (7)	0.0160 (6)	−0.0027 (6)	0.0004 (5)	−0.0063 (5)
C11	0.0141 (6)	0.0192 (6)	0.0297 (8)	0.0033 (5)	−0.0034 (5)	−0.0111 (6)
C12	0.0209 (7)	0.0135 (6)	0.0313 (8)	0.0032 (5)	−0.0068 (6)	−0.0002 (6)
C13	0.0165 (6)	0.0158 (6)	0.0173 (6)	−0.0010 (5)	−0.0030 (5)	0.0010 (5)
C14	0.0139 (6)	0.0143 (6)	0.0195 (6)	0.0020 (5)	−0.0013 (5)	0.0002 (5)
C15	0.0156 (6)	0.0187 (6)	0.0166 (6)	0.0046 (5)	−0.0014 (5)	0.0022 (5)
C16	0.0164 (6)	0.0231 (7)	0.0249 (7)	0.0000 (6)	−0.0046 (5)	0.0024 (6)

Geometric parameters (Å, º) top

O1—C7	1.4217 (17)	C8—C13	1.392 (2)
O1—H1	0.86 (2)	C8—C9	1.393 (2)
C1—C6	1.391 (2)	C9—C10	1.389 (2)
C1—C2	1.3928 (19)	C9—H9	0.95
C1—C7	1.5283 (19)	C10—C11	1.387 (2)
C2—C3	1.388 (2)	C10—H10	0.95
C2—H2	0.95	C11—C12	1.382 (2)
C3—C4	1.385 (2)	C11—H11	0.95
C3—H3	0.95	C12—C13	1.392 (2)
C4—C5	1.386 (2)	C12—H12	0.95
C4—H4	0.95	C13—H13	0.95
C5—C6	1.388 (2)	C14—C15	1.463 (2)
C5—H5	0.95	C14—H14A	0.99
C6—H6	0.95	C14—H14B	0.99
C7—C8	1.5332 (19)	C15—C16	1.190 (2)
C7—C14	1.5460 (19)	C16—H16	0.95

C7—O1—H1	109.5	C13—C8—C7	119.50 (12)
C6—C1—C2	118.63 (12)	C9—C8—C7	121.87 (12)
C6—C1—C7	119.71 (12)	C10—C9—C8	120.54 (13)
C2—C1—C7	121.65 (12)	C10—C9—H9	119.7
C3—C2—C1	120.51 (13)	C8—C9—H9	119.7
C3—C2—H2	119.7	C11—C10—C9	120.60 (14)
C1—C2—H2	119.7	C11—C10—H10	119.7
C4—C3—C2	120.52 (13)	C9—C10—H10	119.7
C4—C3—H3	119.7	C12—C11—C10	119.17 (13)
C2—C3—H3	119.7	C12—C11—H11	120.4
C3—C4—C5	119.30 (13)	C10—C11—H11	120.4
C3—C4—H4	120.3	C11—C12—C13	120.50 (14)
C5—C4—H4	120.3	C11—C12—H12	119.8
C4—C5—C6	120.33 (13)	C13—C12—H12	119.8
C4—C5—H5	119.8	C8—C13—C12	120.65 (14)
C6—C5—H5	119.8	C8—C13—H13	119.7
C5—C6—C1	120.72 (12)	C12—C13—H13	119.7
C5—C6—H6	119.6	C15—C14—C7	110.60 (12)
C1—C6—H6	119.6	C15—C14—H14A	109.5
O1—C7—C1	106.13 (11)	C7—C14—H14A	109.5
O1—C7—C8	110.96 (12)	C15—C14—H14B	109.5
C1—C7—C8	108.58 (11)	C7—C14—H14B	109.5
O1—C7—C14	108.20 (11)	H14A—C14—H14B	108.1
C1—C7—C14	110.76 (11)	C16—C15—C14	176.26 (15)
C8—C7—C14	112.06 (11)	C15—C16—H16	180.0
C13—C8—C9	118.54 (12)

C6—C1—C2—C3	0.50 (19)	C14—C7—C8—C13	142.93 (12)
C7—C1—C2—C3	178.85 (12)	O1—C7—C8—C9	−161.69 (12)
C1—C2—C3—C4	−0.2 (2)	C1—C7—C8—C9	82.05 (15)
C2—C3—C4—C5	−0.3 (2)	C14—C7—C8—C9	−40.62 (17)
C3—C4—C5—C6	0.5 (2)	C13—C8—C9—C10	0.9 (2)
C4—C5—C6—C1	−0.2 (2)	C7—C8—C9—C10	−175.59 (12)
C2—C1—C6—C5	−0.29 (19)	C8—C9—C10—C11	−0.9 (2)
C7—C1—C6—C5	−178.67 (12)	C9—C10—C11—C12	0.0 (2)
C6—C1—C7—O1	−20.69 (16)	C10—C11—C12—C13	1.0 (2)
C2—C1—C7—O1	160.98 (12)	C9—C8—C13—C12	0.1 (2)
C6—C1—C7—C8	98.64 (14)	C7—C8—C13—C12	176.63 (12)
C2—C1—C7—C8	−79.68 (15)	C11—C12—C13—C8	−1.0 (2)
C6—C1—C7—C14	−137.91 (12)	O1—C7—C14—C15	59.66 (14)
C2—C1—C7—C14	43.77 (16)	C1—C7—C14—C15	175.60 (11)
O1—C7—C8—C13	21.86 (17)	C8—C7—C14—C15	−62.99 (15)
C1—C7—C8—C13	−94.40 (14)

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.

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