5,5-Diphenyl-cis-penta-2,4-dienoic acid

Pineda, L.W.; Amey, A.; Cabezas, J.A.

doi:10.1107/S2414314618017996

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 1| January 2019| x181799

https://doi.org/10.1107/S2414314618017996

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5,5-Diphenyl-cis-penta-2,4-dienoic acid

Leslie W. Pineda,^a,^b Adam Amey ^a and Jorge A. Cabezas ^a ^*

^aEscuela de Química, Universidad de Costa Rica, 11501, San José, Costa Rica, and ^bCentro de Electroquímica y Energía Química (CELEQ), Universidad de Costa Rica, 11501, San José, Costa Rica
^*Correspondence e-mail: jorge.cabezas@ucr.ac.cr

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 10 December 2018; accepted 19 December 2018; online 4 January 2018)

In the title compound, C₁₇H₁₄O₂, the dihedral angle between the phenyl rings is 76.52 (7)°. In the crystal, pairwise O—H⋯O hydrogen bonds link the molecules into carboxylic acid inversion dimers.

Keywords: crystal structure; 1,3-dilithiopropyne; pent-2,4-dienoic acid; propargylation.

CCDC reference: 1883168

Structure description

Many 2,4-dienoic acids are widely found in nature and have shown important biological activity (Masi et al., 2014 ). For example, abscisic acid {systematic name: (2Z,4E)-5-[(1S)-1-hydroxy-2,6,6-trimethyl-4-oxocyclohex-2-en-1-yl]-3-methylpenta-2,4-dienoic acid}, the most common 2,4-pentadienoic acid, isolated from cotton fruit (Ohkuma et al., 1963 ), is a plant hormone that plays important developmental processes (Finkelstein 2013 ). It also plays an important role in plant responses to environmental stress and plant pathogens (Zhu, 2002 ; Seo & Koshiba 2002 ). Many methods for the synthesis of this diene system in pent-2,4-dienoic acids have been developed (Huh et al., 1993 ; Bellassoued & Ennigrou 1991 ). In this paper we report a new methodology for the synthesis of the title compound, 1, and its crystal structure.

The crystal structure of 1 has monoclinic symmetry with one molecule in the asymmetric unit: the molecular structure contains two conjugated carbon double bonds (C1=C14) and (C15=C16) in which the former diene fragment at C1 bound to two phenyl-ring substituents and the latter diene moiety further binds at C16 to a carboxylic acid functional group leading to a cis configuration (Fig. 1). The bond lengths of the diene arrangements C1=C14 and C15=C16 are 1.349 (2) Å and 1.346 (2) Å, respectively. The carboxyl group has the following bond lengths: C17—O1 [1.228 (2) Å] and C17—O2 [1.324 (2) Å]. In the crystal, pairwise O2—H2⋯O1 hydrogen-bonding interactions form dimeric arrangements between molecules, forming a loop with an R₂²(8) graph-set motif (Fig. 2 and Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.93	1.74	2.6628 (14)	177
Symmetry code: (i) -x, -y+1, -z.

Figure 1
The title molecule with 50% probability ellipsoids.

Figure 2
Packing of the molecules with O—H⋯O hydrogen bonds shown as green dashed lines.

Synthesis and crystallization

The reaction of propargyl bromide, 2, with n-BuLi in the presence of tetramethylethylenediamine (TMEDA), at −78°C, generated the synthetic equivalent of the dianion 1,3-dilithiopropyne, 3, Fig. 3 (Cabezas et al., 2001 ). Sequential treatment of this dianion, 3, with benzophenone followed by addition of ethyl chloroformate, and warming to room temperature overnight, produced carbonate, 4, in 70% yield. Alkaline hydrolysis of 4, using KOH in methanol, at room temperature for 3 h yielded 5,5-diphenylpent-4-ene-2-ynoic acid, 5, in 87% yield. Hydrogenation of 5, using Lindlar's catalyst yielded 5,5-diphenyl-cis-penta-2,4-dienoic acid, 1, in 97% isolated yield. The overall yield for this synthesis was 59%. Light-yellow blocks were recrystallized from ethyl acetate solution at ambient temperature.

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	C₁₇H₁₄O₂
M_r	250.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	9.0801 (4), 15.4598 (7), 10.0920 (4)
β (°)	109.453 (1)
V (Å³)	1335.81 (10)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.25 × 0.15 × 0.10

Data collection
Diffractometer	Bruker D8 Venture
Absorption correction	Multi-scan (SADABS; Bruker, 2015 )
T_min, T_max	0.713, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	19268, 3081, 2479
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.101, 1.05
No. of reflections	3081
No. of parameters	174
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.33
Computer programs: APEX3 and SAINT (Bruker, 2015), SHELXT (Sheldrick 2015a ), SHELXL2014 (Sheldrick, 2015b ) and Mercury (Macrae et al., 2006 ).

Structural data

CCDC reference: 1883168

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314618017996/hb4275sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618017996/hb4275Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (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).

5,5-Diphenyl-cis-penta-2,4-dienoic acid top

Crystal data top

C₁₇H₁₄O₂	F(000) = 528
M_r = 250.29	D_x = 1.244 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.0801 (4) Å	Cell parameters from 7723 reflections
b = 15.4598 (7) Å	θ = 2.5–27.5°
c = 10.0920 (4) Å	µ = 0.08 mm⁻¹
β = 109.453 (1)°	T = 100 K
V = 1335.81 (10) Å³	Block, light yellow
Z = 4	0.25 × 0.15 × 0.10 mm

Data collection top

Bruker D8 Venture diffractometer	3081 independent reflections
Radiation source: Incoatec Microsource	2479 reflections with I > 2σ(I)
Mirrors monochromator	R_int = 0.037
Detector resolution: 10.4167 pixels mm^-1	θ_max = 27.6°, θ_min = 2.5°
ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −20→20
T_min = 0.713, T_max = 0.746	l = −13→13
19268 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) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0392P)² + 0.6455P] where P = (F_o² + 2F_c²)/3
3081 reflections	(Δ/σ)_max < 0.001
174 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.33 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	0.05901 (11)	0.54513 (7)	0.15632 (10)	0.0237 (2)
O2	−0.18489 (12)	0.50474 (7)	0.03482 (10)	0.0228 (2)
H2	−0.1377 (11)	0.4886 (11)	−0.0300 (16)	0.034*
C1	0.18364 (15)	0.64377 (9)	0.56368 (13)	0.0154 (3)
C2	0.10925 (15)	0.70128 (9)	0.64163 (14)	0.0158 (3)
C3	0.14619 (16)	0.68961 (9)	0.78666 (14)	0.0187 (3)
H3	0.2151	0.6444	0.8327	0.022*
C4	0.08313 (17)	0.74347 (10)	0.86354 (15)	0.0230 (3)
H4	0.1068	0.7341	0.9615	0.028*
C5	−0.01446 (17)	0.81101 (10)	0.79803 (16)	0.0241 (3)
H5	−0.0564	0.8484	0.8512	0.029*
C6	−0.05063 (17)	0.82382 (10)	0.65483 (16)	0.0241 (3)
H6	−0.1172	0.8702	0.6099	0.029*
C7	0.01017 (16)	0.76900 (10)	0.57661 (15)	0.0207 (3)
H7	−0.016	0.7778	0.4783	0.025*
C8	0.35685 (16)	0.63744 (9)	0.62313 (13)	0.0156 (3)
C9	0.44543 (16)	0.71162 (9)	0.67401 (14)	0.0191 (3)
H9	0.3941	0.7653	0.6724	0.023*
C10	0.60701 (17)	0.70804 (10)	0.72673 (15)	0.0224 (3)
H10	0.6658	0.7592	0.7594	0.027*
C11	0.68287 (17)	0.62948 (10)	0.73173 (15)	0.0227 (3)
H11	0.7937	0.6267	0.7676	0.027*
C12	0.59618 (17)	0.55526 (10)	0.68411 (15)	0.0219 (3)
H12	0.6479	0.5013	0.6891	0.026*
C13	0.43436 (16)	0.55893 (9)	0.62916 (14)	0.0184 (3)
H13	0.3761	0.5077	0.5955	0.022*
C14	0.10456 (16)	0.60064 (9)	0.44511 (14)	0.0168 (3)
H14	0.1645	0.5701	0.3991	0.02*
C15	−0.06333 (16)	0.59693 (9)	0.38208 (14)	0.0180 (3)
H15	−0.1222	0.6177	0.4376	0.022*
C16	−0.14545 (16)	0.56720 (9)	0.25332 (14)	0.0180 (3)
H16	−0.2558	0.5646	0.2294	0.022*
C17	−0.07883 (16)	0.53848 (9)	0.14689 (14)	0.0170 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0181 (5)	0.0348 (6)	0.0173 (5)	−0.0027 (4)	0.0048 (4)	−0.0075 (4)
O2	0.0200 (5)	0.0319 (6)	0.0148 (5)	−0.0042 (4)	0.0035 (4)	−0.0056 (4)
C1	0.0170 (7)	0.0164 (7)	0.0133 (6)	0.0015 (5)	0.0058 (5)	0.0031 (5)
C2	0.0138 (7)	0.0185 (7)	0.0151 (6)	−0.0015 (5)	0.0046 (5)	−0.0031 (5)
C3	0.0170 (7)	0.0218 (7)	0.0162 (7)	−0.0013 (6)	0.0042 (5)	−0.0002 (5)
C4	0.0223 (8)	0.0321 (8)	0.0163 (7)	−0.0047 (6)	0.0086 (6)	−0.0062 (6)
C5	0.0181 (7)	0.0290 (8)	0.0283 (8)	−0.0036 (6)	0.0121 (6)	−0.0139 (6)
C6	0.0172 (7)	0.0251 (8)	0.0277 (8)	0.0047 (6)	0.0045 (6)	−0.0047 (6)
C7	0.0189 (7)	0.0254 (8)	0.0158 (7)	0.0019 (6)	0.0030 (6)	−0.0024 (6)
C8	0.0167 (7)	0.0211 (7)	0.0102 (6)	0.0010 (5)	0.0061 (5)	−0.0001 (5)
C9	0.0221 (7)	0.0190 (7)	0.0188 (7)	0.0009 (6)	0.0103 (6)	−0.0015 (5)
C10	0.0226 (8)	0.0264 (8)	0.0206 (7)	−0.0063 (6)	0.0102 (6)	−0.0046 (6)
C11	0.0156 (7)	0.0342 (9)	0.0181 (7)	0.0003 (6)	0.0053 (6)	−0.0005 (6)
C12	0.0198 (7)	0.0243 (8)	0.0210 (7)	0.0060 (6)	0.0061 (6)	0.0003 (6)
C13	0.0197 (7)	0.0191 (7)	0.0165 (7)	−0.0003 (6)	0.0061 (5)	−0.0024 (5)
C14	0.0188 (7)	0.0174 (7)	0.0151 (6)	0.0032 (5)	0.0070 (5)	0.0002 (5)
C15	0.0203 (7)	0.0171 (7)	0.0178 (7)	0.0023 (5)	0.0081 (6)	0.0009 (5)
C16	0.0147 (7)	0.0188 (7)	0.0192 (7)	0.0006 (5)	0.0041 (5)	0.0013 (5)
C17	0.0182 (7)	0.0147 (6)	0.0150 (7)	0.0001 (5)	0.0015 (5)	0.0011 (5)

Geometric parameters (Å, º) top

O1—C17	1.2275 (17)	C8—C13	1.3943 (19)
O2—C17	1.3241 (16)	C8—C9	1.397 (2)
O2—H2	0.928 (19)	C9—C10	1.385 (2)
C1—C14	1.3489 (19)	C9—H9	0.95
C1—C8	1.4882 (19)	C10—C11	1.389 (2)
C1—C2	1.4898 (18)	C10—H10	0.95
C2—C7	1.394 (2)	C11—C12	1.384 (2)
C2—C3	1.4000 (19)	C11—H11	0.95
C3—C4	1.385 (2)	C12—C13	1.388 (2)
C3—H3	0.95	C12—H12	0.95
C4—C5	1.386 (2)	C13—H13	0.95
C4—H4	0.95	C14—C15	1.444 (2)
C5—C6	1.385 (2)	C14—H14	0.95
C5—H5	0.95	C15—C16	1.3455 (19)
C6—C7	1.392 (2)	C15—H15	0.95
C6—H6	0.95	C16—C17	1.466 (2)
C7—H7	0.95	C16—H16	0.95

C17—O2—H2	109.5	C10—C9—H9	119.5
C14—C1—C8	120.27 (12)	C8—C9—H9	119.5
C14—C1—C2	124.22 (12)	C9—C10—C11	119.86 (14)
C8—C1—C2	115.50 (11)	C9—C10—H10	120.1
C7—C2—C3	118.77 (13)	C11—C10—H10	120.1
C7—C2—C1	122.32 (12)	C12—C11—C10	119.64 (13)
C3—C2—C1	118.83 (12)	C12—C11—H11	120.2
C4—C3—C2	120.55 (13)	C10—C11—H11	120.2
C4—C3—H3	119.7	C11—C12—C13	120.59 (14)
C2—C3—H3	119.7	C11—C12—H12	119.7
C3—C4—C5	120.22 (13)	C13—C12—H12	119.7
C3—C4—H4	119.9	C12—C13—C8	120.31 (13)
C5—C4—H4	119.9	C12—C13—H13	119.8
C6—C5—C4	119.80 (13)	C8—C13—H13	119.8
C6—C5—H5	120.1	C1—C14—C15	125.61 (13)
C4—C5—H5	120.1	C1—C14—H14	117.2
C5—C6—C7	120.24 (14)	C15—C14—H14	117.2
C5—C6—H6	119.9	C16—C15—C14	127.09 (13)
C7—C6—H6	119.9	C16—C15—H15	116.5
C6—C7—C2	120.41 (13)	C14—C15—H15	116.5
C6—C7—H7	119.8	C15—C16—C17	125.44 (13)
C2—C7—H7	119.8	C15—C16—H16	117.3
C13—C8—C9	118.58 (12)	C17—C16—H16	117.3
C13—C8—C1	121.67 (12)	O1—C17—O2	122.14 (13)
C9—C8—C1	119.75 (12)	O1—C17—C16	125.22 (12)
C10—C9—C8	121.01 (13)	O2—C17—C16	112.64 (12)

C14—C1—C2—C7	−53.4 (2)	C2—C1—C8—C9	−41.06 (17)
C8—C1—C2—C7	125.11 (14)	C13—C8—C9—C10	1.3 (2)
C14—C1—C2—C3	129.82 (15)	C1—C8—C9—C10	−178.39 (12)
C8—C1—C2—C3	−51.65 (17)	C8—C9—C10—C11	−1.2 (2)
C7—C2—C3—C4	1.1 (2)	C9—C10—C11—C12	−0.1 (2)
C1—C2—C3—C4	178.03 (13)	C10—C11—C12—C13	1.1 (2)
C2—C3—C4—C5	−1.6 (2)	C11—C12—C13—C8	−0.9 (2)
C3—C4—C5—C6	0.9 (2)	C9—C8—C13—C12	−0.3 (2)
C4—C5—C6—C7	0.2 (2)	C1—C8—C13—C12	179.43 (12)
C5—C6—C7—C2	−0.7 (2)	C8—C1—C14—C15	175.75 (13)
C3—C2—C7—C6	0.0 (2)	C2—C1—C14—C15	−5.8 (2)
C1—C2—C7—C6	−176.78 (13)	C1—C14—C15—C16	168.04 (14)
C14—C1—C8—C13	−42.21 (19)	C14—C15—C16—C17	−5.0 (2)
C2—C1—C8—C13	139.20 (13)	C15—C16—C17—O1	−7.0 (2)
C14—C1—C8—C9	137.53 (14)	C15—C16—C17—O2	173.96 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.93	1.74	2.6628 (14)	177

Symmetry code: (i) −x, −y+1, −z.

Acknowledgements

CELEQ is thanked for supplying liquid nitrogen for the X-ray measurements.

Funding information

Funding for this research was provided by: Vicerrectoría de Investigación, Universidad de Costa Rica (UCR).

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