2,5-Bis(4-methyl­phen­yl)-4-oxopenta­noic acid

Wang, J.; Zhuang, X.; Hou, Y.

doi:10.1107/S1600536810037323

organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2621

doi:10.1107/S1600536810037323

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2,5-Bis(4-methylphenyl)-4-oxopentanoic acid

Jun Wang,^a Xiaomei Zhuang ^a ^* and Yong Hou ^a

^aZhongshan Polytechnic, Zhongshan, Guangdong 528404, People's Republic of China
^*Correspondence e-mail: wangjun7203@126.com

(Received 15 September 2010; accepted 17 September 2010; online 25 September 2010)

The title compound, C₁₉H₂₀O₃, was obtained from 1,4-bis(4-methylphenyl)but-3-yn-2-one in the presence of carbon monoxide by Ni(CN)₂ catalysis in a basic aqueous medium. Intermolecular O—H⋯O hydrogen bonds lead to the formation of hydrogen-bonded carboxylic acid dimers [graph-set motif R²₂(8)]. Weak C—H⋯O hydrogen bonds between neighbouring dimers further extend the structure to give rise to a three-dimensional supramolecular network.

Related literature

For general background to transition metal-mediated carbonylation reactions, see: Collins (1999 ); Arzoumanian et al. (1995 ). For a similar structure, see: Garcia-Gutierrez et al. (2004 ). For bond length values, see: Allen et al. (1987 ). For hydrogen-bonding motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₉H₂₀O₃
M_r = 296.35
Monoclinic, P 2₁ /c
a = 11.846 (2) Å
b = 13.155 (3) Å
c = 11.755 (2) Å
β = 115.98 (3)°
V = 1646.7 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.25 × 0.22 × 0.19 mm

Data collection

Bruker APEXII area-detector diffractometer
12947 measured reflections
2956 independent reflections
1474 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.173
S = 1.01
2956 reflections
202 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17⋯O1ⁱ	0.93	2.50	3.418 (4)	169
C15—H15⋯O2ⁱⁱ	0.93	2.56	3.452 (4)	160
O2—H2A⋯O3ⁱⁱⁱ	0.82	1.83	2.638 (2)	169
Symmetry codes: (i) -x, -y, -z; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810037323/zl2309sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810037323/zl2309Isup2.hkl

checkCIF report

Comment top

Transition-metal-mediated carbonylation reactions are of great research interest in recent years (Collins, 1999). Amongst the many metal-mediated syntheses used, catalysis by nickel cyanide in aqueous media under phase transfer conditions has attracted particular attention (Arzoumanian et al., 1995) and numerous lactones and their hydrolysis products have been synthesized using this system. Herein, we chose 1,4-di(4-methylbenzyl)but-3-yn-2-one as a carbonylation substrate to be reacted in the presence of Ni(CN)₂ and carbon monoxide in a biphasic toluene/basic aqueous medium to give the title compound.

The structure of the title compound is depicted in Fig. 1. The C—C bond lengths show normal values (Allen et al., 1987), and the C—O and C═O bond lengths are comparable to those observed in simliar structures (Garcia-Gutierrez et al., 2004). The molecules form dimers with neighboring molecules through O—H···O hydrogen bonding with an R²₂(8) graph set motif (Bernstein et al., 1995). These dimers are further linked by C—H···O hydrogen bonds (Table 1) to form a three-dimensional supramolecular network (Fig. 2).

Related literature top

For general background on transition metal-mediated carbonylation reactions, see: Collins (1999); Arzoumanian et al. (1995). For a similar structure, see: Garcia-Gutierrez et al. (2004). For bond length values, see: Allen et al. (1987). For hydrogen-bonding motifs, see: Bernstein et al. (1995).

Experimental top

A typical experiment was performed as follows: in a round-bottomed flask toluene (25 ml) and 1 M aqueous NaOH (10 ml) were degassed and saturated with CO under atmospheric pressure before Ni(CN)₂.4H₂O (1.0 mmol) and tetrabutylammonium bromide (0.3 mmol) were introduced, and the mixture was kept at room temperature overnight with stirring while CO was slowly (2–3 min) bubbled through the solution. To the yellow two-phase mixture was then added 10 mmol of 1,4-di(4-methylbenzyl)but-3-yn-2-one, and stirring and flow of CO at a flow rate of 3 ml min^-1 were maintained for 5 h at 393 K. At the end of the reaction, ethyl ether (2 × 20 ml) was used to eliminate the impurities. The aqueous phase was acidified with diluted HCl at pH = 1. Ethyl ether (2 × 20 ml) was used to extract the product. The organic phase was dried over Na₂SO₄ and evaporated to obtain a yellow powder. During recrystallization, the yellow block crystals were obtained by slow evaporation of the solvent with a yield of 68%. m.p. 476–478 K; IR (KBr) cm^-1: 3052, 2980, 2948, 1716, 1705, 1669, 1607, 1573, 1465, 1416, 1379, 1345, 1285, 1246, 1232, 1217, 1186, 1150, 1068, 1044, 995, 972, 850.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP represention of atom numbering diagram for the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. View of the three-dimensional structure of the title compound. H-bonds are shown as dashed lines.

2,5-Bis(4-methylphenyl)-4-oxopentanoic acid top

Crystal data top

C₁₉H₂₀O₃	F(000) = 632
M_r = 296.35	D_x = 1.195 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2279 reflections
a = 11.846 (2) Å	θ = 2.3–28.0°
b = 13.155 (3) Å	µ = 0.08 mm⁻¹
c = 11.755 (2) Å	T = 293 K
β = 115.98 (3)°	Block, yellow
V = 1646.7 (7) Å³	0.25 × 0.22 × 0.19 mm
Z = 4

Data collection top

Bruker APEXII area-detector diffractometer	1474 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.062
Graphite monochromator	θ_max = 25.2°, θ_min = 3.1°
ϕ and ω scan	h = −14→14
12947 measured reflections	k = −15→15
2956 independent reflections	l = −14→14

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.173	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.085P)²] where P = (F_o² + 2F_c²)/3
2956 reflections	(Δ/σ)_max < 0.001
202 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₉H₂₀O₃	V = 1646.7 (7) Å³
M_r = 296.35	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.846 (2) Å	µ = 0.08 mm⁻¹
b = 13.155 (3) Å	T = 293 K
c = 11.755 (2) Å	0.25 × 0.22 × 0.19 mm
β = 115.98 (3)°

Data collection top

Bruker APEXII area-detector diffractometer	1474 reflections with I > 2σ(I)
12947 measured reflections	R_int = 0.062
2956 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.173	H-atom parameters constrained
S = 1.01	Δρ_max = 0.24 e Å⁻³
2956 reflections	Δρ_min = −0.18 e Å⁻³
202 parameters

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
C1	0.2848 (2)	0.06339 (18)	0.6978 (3)	0.0586 (7)
C2	0.3764 (2)	0.1318 (2)	0.7725 (3)	0.0695 (8)
H2	0.4156	0.1729	0.7360	0.083*
C3	0.4101 (3)	0.1396 (2)	0.9004 (3)	0.0772 (9)
H3	0.4722	0.1858	0.9485	0.093*
C4	0.3548 (3)	0.0817 (2)	0.9587 (3)	0.0744 (8)
C5	0.2638 (3)	0.0149 (3)	0.8837 (3)	0.0859 (9)
H5	0.2239	−0.0254	0.9201	0.103*
C6	0.2299 (3)	0.0057 (2)	0.7571 (3)	0.0758 (8)
H6	0.1680	−0.0409	0.7099	0.091*
C7	0.3949 (4)	0.0898 (3)	1.0989 (3)	0.1073 (12)
H7A	0.4565	0.1427	1.1337	0.161*
H7B	0.4304	0.0263	1.1388	0.161*
H7C	0.3232	0.1057	1.1136	0.161*
C8	0.2475 (2)	0.05361 (18)	0.5580 (2)	0.0568 (7)
H8	0.1909	−0.0049	0.5272	0.068*
C9	0.3590 (2)	0.0320 (2)	0.5332 (3)	0.0581 (7)
C10	0.1766 (2)	0.1458 (2)	0.4817 (3)	0.0654 (7)
H10A	0.1111	0.1638	0.5065	0.078*
H10B	0.2341	0.2028	0.5021	0.078*
C11	0.1187 (2)	0.1287 (2)	0.3424 (3)	0.0617 (7)
C12	0.0992 (3)	0.2191 (2)	0.2583 (3)	0.0764 (8)
H12A	0.0774	0.2768	0.2961	0.092*
H12B	0.1783	0.2348	0.2563	0.092*
C13	0.0008 (2)	0.20819 (18)	0.1251 (3)	0.0604 (7)
C14	−0.1074 (3)	0.2653 (2)	0.0815 (3)	0.0827 (9)
H14	−0.1173	0.3129	0.1349	0.099*
C15	−0.2006 (3)	0.2536 (2)	−0.0386 (4)	0.0892 (10)
H15	−0.2723	0.2937	−0.0646	0.107*
C16	−0.1916 (3)	0.1845 (2)	−0.1219 (3)	0.0729 (8)
C17	−0.0825 (3)	0.1291 (2)	−0.0809 (3)	0.0678 (8)
H17	−0.0718	0.0832	−0.1355	0.081*
C18	0.0115 (2)	0.14094 (19)	0.0405 (3)	0.0638 (7)
H18	0.0843	0.1023	0.0659	0.077*
C19	−0.2969 (3)	0.1693 (3)	−0.2526 (4)	0.1142 (13)
H19A	−0.2762	0.1145	−0.2939	0.171*
H19B	−0.3088	0.2305	−0.3010	0.171*
H19C	−0.3729	0.1533	−0.2460	0.171*
O1	0.0871 (2)	0.04379 (15)	0.3000 (2)	0.0947 (7)
O2	0.41394 (17)	−0.05500 (14)	0.5781 (2)	0.0763 (6)
H2A	0.4777	−0.0597	0.5674	0.114*
O3	0.39643 (17)	0.08983 (15)	0.4773 (2)	0.0817 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0534 (14)	0.0674 (16)	0.0574 (18)	0.0026 (11)	0.0266 (13)	−0.0028 (13)
C2	0.0662 (17)	0.0777 (18)	0.065 (2)	−0.0016 (13)	0.0293 (15)	−0.0019 (15)
C3	0.0674 (17)	0.088 (2)	0.064 (2)	0.0083 (14)	0.0171 (16)	−0.0111 (16)
C4	0.085 (2)	0.085 (2)	0.0540 (19)	0.0263 (16)	0.0306 (16)	0.0051 (16)
C5	0.105 (2)	0.097 (2)	0.073 (3)	0.0023 (18)	0.055 (2)	0.0100 (18)
C6	0.0804 (19)	0.087 (2)	0.069 (2)	−0.0133 (14)	0.0415 (17)	−0.0067 (16)
C7	0.132 (3)	0.126 (3)	0.060 (2)	0.048 (2)	0.039 (2)	0.010 (2)
C8	0.0558 (14)	0.0617 (14)	0.0549 (17)	−0.0005 (11)	0.0262 (12)	−0.0015 (12)
C9	0.0578 (15)	0.0647 (15)	0.0563 (17)	0.0003 (12)	0.0294 (13)	−0.0026 (13)
C10	0.0601 (15)	0.0771 (17)	0.0588 (19)	0.0056 (12)	0.0258 (13)	−0.0081 (13)
C11	0.0621 (15)	0.0671 (17)	0.0547 (18)	−0.0022 (12)	0.0245 (13)	−0.0054 (13)
C12	0.086 (2)	0.0749 (18)	0.064 (2)	−0.0135 (14)	0.0293 (16)	−0.0020 (15)
C13	0.0696 (16)	0.0574 (14)	0.0578 (18)	−0.0044 (12)	0.0312 (14)	0.0008 (13)
C14	0.095 (2)	0.084 (2)	0.074 (2)	0.0215 (16)	0.0407 (19)	−0.0013 (16)
C15	0.080 (2)	0.103 (2)	0.083 (3)	0.0331 (17)	0.0347 (19)	0.016 (2)
C16	0.0686 (17)	0.0887 (19)	0.060 (2)	−0.0010 (15)	0.0266 (15)	0.0068 (16)
C17	0.0831 (19)	0.0671 (17)	0.058 (2)	−0.0030 (14)	0.0355 (16)	−0.0034 (13)
C18	0.0693 (16)	0.0627 (16)	0.064 (2)	0.0077 (12)	0.0336 (15)	0.0056 (13)
C19	0.083 (2)	0.169 (4)	0.076 (3)	−0.010 (2)	0.021 (2)	0.009 (2)
O1	0.1269 (17)	0.0755 (14)	0.0615 (14)	−0.0101 (12)	0.0226 (12)	−0.0026 (11)
O2	0.0787 (13)	0.0734 (12)	0.0948 (17)	0.0158 (9)	0.0547 (12)	0.0179 (11)
O3	0.0835 (14)	0.0767 (12)	0.1091 (19)	0.0139 (9)	0.0646 (13)	0.0223 (12)

Geometric parameters (Å, º) top

C1—C6	1.372 (4)	C10—H10B	0.9700
C1—C2	1.387 (3)	C11—O1	1.214 (3)
C1—C8	1.508 (4)	C11—C12	1.498 (4)
C2—C3	1.380 (4)	C12—C13	1.494 (4)
C2—H2	0.9300	C12—H12A	0.9700
C3—C4	1.368 (4)	C12—H12B	0.9700
C3—H3	0.9300	C13—C14	1.376 (4)
C4—C5	1.371 (4)	C13—C18	1.378 (4)
C4—C7	1.506 (4)	C14—C15	1.367 (4)
C5—C6	1.366 (4)	C14—H14	0.9300
C5—H5	0.9300	C15—C16	1.375 (4)
C6—H6	0.9300	C15—H15	0.9300
C7—H7A	0.9600	C16—C17	1.374 (4)
C7—H7B	0.9600	C16—C19	1.509 (4)
C7—H7C	0.9600	C17—C18	1.381 (4)
C8—C9	1.499 (3)	C17—H17	0.9300
C8—C10	1.523 (3)	C18—H18	0.9300
C8—H8	0.9800	C19—H19A	0.9600
C9—O3	1.209 (3)	C19—H19B	0.9600
C9—O2	1.308 (3)	C19—H19C	0.9600
C10—C11	1.489 (4)	O2—H2A	0.8200
C10—H10A	0.9700

C6—C1—C2	116.8 (3)	C8—C10—H10B	108.9
C6—C1—C8	121.9 (2)	H10A—C10—H10B	107.7
C2—C1—C8	121.3 (3)	O1—C11—C10	120.1 (3)
C3—C2—C1	120.7 (3)	O1—C11—C12	121.9 (3)
C3—C2—H2	119.6	C10—C11—C12	118.0 (2)
C1—C2—H2	119.6	C13—C12—C11	116.1 (2)
C4—C3—C2	122.0 (3)	C13—C12—H12A	108.3
C4—C3—H3	119.0	C11—C12—H12A	108.3
C2—C3—H3	119.0	C13—C12—H12B	108.3
C3—C4—C5	116.7 (3)	C11—C12—H12B	108.3
C3—C4—C7	121.2 (3)	H12A—C12—H12B	107.4
C5—C4—C7	122.1 (3)	C14—C13—C18	116.5 (3)
C6—C5—C4	122.0 (3)	C14—C13—C12	120.6 (3)
C6—C5—H5	119.0	C18—C13—C12	122.8 (2)
C4—C5—H5	119.0	C15—C14—C13	121.5 (3)
C5—C6—C1	121.7 (3)	C15—C14—H14	119.3
C5—C6—H6	119.1	C13—C14—H14	119.3
C1—C6—H6	119.1	C14—C15—C16	122.0 (3)
C4—C7—H7A	109.5	C14—C15—H15	119.0
C4—C7—H7B	109.5	C16—C15—H15	119.0
H7A—C7—H7B	109.5	C17—C16—C15	117.1 (3)
C4—C7—H7C	109.5	C17—C16—C19	121.2 (3)
H7A—C7—H7C	109.5	C15—C16—C19	121.7 (3)
H7B—C7—H7C	109.5	C16—C17—C18	120.8 (3)
C9—C8—C1	111.4 (2)	C16—C17—H17	119.6
C9—C8—C10	110.0 (2)	C18—C17—H17	119.6
C1—C8—C10	113.4 (2)	C13—C18—C17	122.0 (2)
C9—C8—H8	107.3	C13—C18—H18	119.0
C1—C8—H8	107.3	C17—C18—H18	119.0
C10—C8—H8	107.3	C16—C19—H19A	109.5
O3—C9—O2	122.2 (2)	C16—C19—H19B	109.5
O3—C9—C8	123.4 (2)	H19A—C19—H19B	109.5
O2—C9—C8	114.4 (2)	C16—C19—H19C	109.5
C11—C10—C8	113.4 (2)	H19A—C19—H19C	109.5
C11—C10—H10A	108.9	H19B—C19—H19C	109.5
C8—C10—H10A	108.9	C9—O2—H2A	109.5
C11—C10—H10B	108.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···O1ⁱ	0.93	2.50	3.418 (4)	169
C15—H15···O2ⁱⁱ	0.93	2.56	3.452 (4)	160
O2—H2A···O3ⁱⁱⁱ	0.82	1.83	2.638 (2)	169

Symmetry codes: (i) −x, −y, −z; (ii) −x, y+1/2, −z+1/2; (iii) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₉H₂₀O₃
M_r	296.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.846 (2), 13.155 (3), 11.755 (2)
β (°)	115.98 (3)
V (Å³)	1646.7 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.25 × 0.22 × 0.19

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	12947, 2956, 1474
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.173, 1.01
No. of reflections	2956
No. of parameters	202
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.18

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···O1ⁱ	0.93	2.50	3.418 (4)	169.2
C15—H15···O2ⁱⁱ	0.93	2.56	3.452 (4)	160.1
O2—H2A···O3ⁱⁱⁱ	0.82	1.83	2.638 (2)	169.0

Symmetry codes: (i) −x, −y, −z; (ii) −x, y+1/2, −z+1/2; (iii) −x+1, −y, −z+1.

Acknowledgements

The work was supported by Zhongshan Polytechnic.

References

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