Isopropyl 3-(3,4-dihydroxy­phen­yl)-2-hydroxy­propanoate

Nan, Y.-F.; Zhang, Q.-Z.; Shen, X.-J.; Zhao, X.-F.; Zheng, X.-H.

doi:10.1107/S1600536810013334

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page o1105

https://doi.org/10.1107/S1600536810013334

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Isopropyl 3-(3,4-dihydroxyphenyl)-2-hydroxypropanoate

Ye-Fei Nan,^a Qun-Zheng Zhang,^b Xu-Ji Shen,^a Xin-Feng Zhao ^a and Xiao-Hui Zheng ^a ^*

^aCollege of Life Scineces, Northwest University, Xi'an 710069, People's Republic of China, and ^bCollege of Chemistry & Chemical Engineering, Xi'an Shiyou University, Xi'an 710065, People's Republic of China
^*Correspondence e-mail: zhengxh@nwu.edu.cn

(Received 16 March 2010; accepted 10 April 2010; online 17 April 2010)

The title compound, C₁₂H₁₆O₅, is a derivative of β-(3,4-dihydroxyphenyl)-α-hydroxy acid. The crystal packing is stabilized by intermolecular O—H⋯O hydrogen bonds.

Related literature

For the antioxidant properties and vasorelaxant activity of the title compound, see: Tian et al. (2008 ); Wang et al. (2008 ). For the preparation, see: Zhang et al. (2009 ).

Experimental

Crystal data

C₁₂H₁₆O₅
M_r = 240.25
Monoclinic, P 2₁ /n
a = 5.7691 (13) Å
b = 14.271 (3) Å
c = 14.955 (3) Å
β = 96.360 (3)°
V = 1223.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.38 × 0.27 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
5934 measured reflections
2174 independent reflections
1598 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.106
S = 1.14
2174 reflections
159 parameters
H-atom parameters constrained
Δρ_max = 0.18 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
O1—H1⋯O4ⁱ	0.82	1.96	2.7621 (14)	164
O2—H2⋯O3ⁱⁱ	0.82	1.93	2.7417 (15)	169
O3—H3⋯O1ⁱⁱⁱ	0.82	2.00	2.7832 (14)	160
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[-x+{\script{5\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810013334/jh2138sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810013334/jh2138Isup2.hkl

checkCIF report

Comment top

The antioxidant property (Tian et al., 2008) and vasorelaxant activity (Wang et al., 2008) of the title compound (I) is already described. At 296 K, X-ray structure analysis was carried out in order to structurally characterised (I). The molecular structure of the title compound and the atom-numbering scheme are shown in Fig.1. In the Fig.1, the hydrogen atoms are omitted for clarity. As shown in Fig.2, both the carbonyl oxygen and the hydroxyl oxygen form hydrogen bonds with the hydrogen of the hydroxyl in another moleculars. The distance of O1 and O4 is 2.7622 (14)/%A. The distance is longer than that between O2 and O3(2.7417/%A), shorter than O3 and O1(2.7832/%A). All the data, listed in table 1 suggest strong hydrogen bond interactions.

Related literature top

For the antioxidant properties and vasorelaxant activity of the title compound, see: Tian et al. (2008); Wang et al. (2008). For the preparation, see: Zhang et al. (2009).

Experimental top

The synthesis of the crude product was carried out according to reported methods(Zhang et al., 2009). The title compound was crystalised from ether and water at room temperature. Spectroscopic analysis: IR(KBr, χm^-1): 3256, 2952, 1678, 1656; ¹H NMR (DMSO, δ, p.p.m.): 12.389 (s, 1 H), 9.492 (s, 1 H), 9.316 (s, 1 H), 7.286—7.282 (d, 1 H), 7.196 (s, 1 H), 7.088—7.068 (m, 1 H), 6.797—6.781 (d, 1 H), 3.771 (s, 3 H), 1.985 (s, 3 H).

Structure description top

For the antioxidant properties and vasorelaxant activity of the title compound, see: Tian et al. (2008); Wang et al. (2008). For the preparation, see: Zhang et al. (2009).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing of (I), viewed down the a axis, molecules are connected by O—H···O hydrogen bonds shown as dashed lines.

Isopropyl 3-(3,4-dihydroxyphenyl)-2-hydroxypropanoate top

Crystal data top

C₁₂H₁₆O₅	D_x = 1.304 Mg m⁻³
M_r = 240.25	Melting point: 360 K
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 5.7691 (13) Å	Cell parameters from 2102 reflections
b = 14.271 (3) Å	θ = 2.7–25.9°
c = 14.955 (3) Å	µ = 0.10 mm⁻¹
β = 96.360 (3)°	T = 296 K
V = 1223.7 (5) Å³	Block, colorless
Z = 4	0.38 × 0.27 × 0.18 mm
F(000) = 512

Data collection top

Bruker SMART CCD area-detector diffractometer	1598 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.029
Graphite monochromator	θ_max = 25.1°, θ_min = 2.0°
phi and ω scans	h = −6→6
5934 measured reflections	k = −17→9
2174 independent reflections	l = −17→17

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0576P)²] where P = (F_o² + 2F_c²)/3
2174 reflections	(Δ/σ)_max < 0.001
159 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₂H₁₆O₅	V = 1223.7 (5) Å³
M_r = 240.25	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.7691 (13) Å	µ = 0.10 mm⁻¹
b = 14.271 (3) Å	T = 296 K
c = 14.955 (3) Å	0.38 × 0.27 × 0.18 mm
β = 96.360 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1598 reflections with I > 2σ(I)
5934 measured reflections	R_int = 0.029
2174 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.14	Δρ_max = 0.18 e Å⁻³
2174 reflections	Δρ_min = −0.18 e Å⁻³
159 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 > σ(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
O1	0.71641 (18)	0.75521 (7)	0.11545 (6)	0.0508 (3)
H1	0.6220	0.7390	0.0733	0.076*
O2	1.09466 (18)	0.79570 (7)	0.22404 (8)	0.0554 (3)
H2	1.2317	0.8059	0.2423	0.083*
O3	0.94395 (17)	0.34163 (7)	0.23630 (6)	0.0457 (3)
H3	0.8648	0.3203	0.2738	0.068*
O4	0.5296 (2)	0.29738 (8)	0.04573 (8)	0.0709 (4)
O5	0.77917 (17)	0.20274 (7)	0.12753 (6)	0.0464 (3)
C1	0.8694 (2)	0.68321 (10)	0.13822 (9)	0.0384 (4)
C2	1.0709 (2)	0.70525 (10)	0.19423 (10)	0.0427 (4)
C3	1.2329 (3)	0.63583 (11)	0.21636 (11)	0.0535 (4)
H3A	1.3698	0.6499	0.2527	0.064*
C4	1.1939 (3)	0.54492 (11)	0.18498 (11)	0.0518 (4)
H4	1.3058	0.4991	0.2004	0.062*
C5	0.9928 (2)	0.52155 (10)	0.13152 (9)	0.0411 (4)
C6	0.8304 (3)	0.59214 (10)	0.10876 (9)	0.0405 (4)
H6	0.6928	0.5777	0.0730	0.049*
C7	0.9418 (3)	0.42345 (10)	0.09809 (9)	0.0461 (4)
H7A	1.0881	0.3911	0.0939	0.055*
H7B	0.8589	0.4265	0.0381	0.055*
C8	0.7973 (2)	0.36720 (10)	0.15824 (9)	0.0395 (4)
H8	0.6727	0.4075	0.1760	0.047*
C9	0.6870 (3)	0.28507 (11)	0.10523 (10)	0.0439 (4)
C10	0.6941 (3)	0.12093 (10)	0.07388 (10)	0.0504 (4)
H10	0.5254	0.1266	0.0577	0.061*
C11	0.7441 (4)	0.03703 (11)	0.13364 (12)	0.0705 (6)
H11A	0.6708	0.0450	0.1877	0.106*
H11B	0.9096	0.0308	0.1486	0.106*
H11C	0.6840	−0.0183	0.1027	0.106*
C12	0.8141 (4)	0.11835 (14)	−0.01037 (13)	0.0812 (6)
H12A	0.9798	0.1149	0.0054	0.122*
H12B	0.7768	0.1741	−0.0449	0.122*
H12C	0.7625	0.0644	−0.0454	0.122*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0510 (7)	0.0484 (7)	0.0490 (6)	0.0097 (5)	−0.0127 (5)	−0.0090 (5)
O2	0.0500 (7)	0.0482 (7)	0.0644 (8)	−0.0019 (5)	−0.0092 (6)	−0.0115 (5)
O3	0.0503 (6)	0.0477 (7)	0.0368 (5)	−0.0044 (5)	−0.0051 (5)	0.0048 (4)
O4	0.0797 (9)	0.0563 (8)	0.0668 (8)	0.0092 (6)	−0.0370 (7)	−0.0063 (6)
O5	0.0533 (6)	0.0363 (6)	0.0468 (6)	0.0017 (5)	−0.0070 (5)	−0.0023 (4)
C1	0.0381 (8)	0.0432 (9)	0.0330 (7)	0.0041 (6)	0.0004 (6)	0.0008 (6)
C2	0.0434 (9)	0.0430 (10)	0.0411 (8)	−0.0032 (7)	0.0023 (7)	−0.0023 (6)
C3	0.0421 (9)	0.0515 (11)	0.0631 (10)	−0.0005 (8)	−0.0113 (7)	0.0021 (8)
C4	0.0460 (9)	0.0482 (10)	0.0595 (10)	0.0067 (8)	−0.0022 (8)	0.0076 (8)
C5	0.0464 (9)	0.0416 (9)	0.0360 (7)	0.0005 (7)	0.0076 (7)	0.0052 (6)
C6	0.0415 (8)	0.0470 (9)	0.0321 (7)	−0.0023 (7)	−0.0006 (6)	0.0000 (6)
C7	0.0558 (10)	0.0454 (9)	0.0376 (8)	0.0036 (7)	0.0073 (7)	0.0008 (7)
C8	0.0418 (8)	0.0389 (9)	0.0369 (8)	0.0040 (6)	0.0001 (6)	0.0003 (6)
C9	0.0472 (9)	0.0419 (9)	0.0404 (8)	0.0041 (7)	−0.0044 (7)	0.0004 (6)
C10	0.0579 (10)	0.0417 (9)	0.0499 (9)	−0.0054 (7)	−0.0021 (7)	−0.0093 (7)
C11	0.1035 (15)	0.0405 (10)	0.0672 (11)	−0.0069 (10)	0.0076 (11)	−0.0050 (8)
C12	0.1136 (17)	0.0685 (13)	0.0647 (11)	0.0007 (12)	0.0244 (11)	−0.0088 (10)

Geometric parameters (Å, º) top

O1—C1	1.3725 (16)	C5—C7	1.505 (2)
O1—H1	0.8200	C6—H6	0.9300
O2—C2	1.3676 (17)	C7—C8	1.5212 (19)
O2—H2	0.8200	C7—H7A	0.9700
O3—C8	1.4116 (16)	C7—H7B	0.9700
O3—H3	0.8200	C8—C9	1.515 (2)
O4—C9	1.2119 (17)	C8—H8	0.9800
O5—C9	1.3172 (17)	C10—C11	1.503 (2)
O5—C10	1.4698 (17)	C10—C12	1.504 (2)
C1—C6	1.3827 (19)	C10—H10	0.9800
C1—C2	1.392 (2)	C11—H11A	0.9600
C2—C3	1.377 (2)	C11—H11B	0.9600
C3—C4	1.389 (2)	C11—H11C	0.9600
C3—H3A	0.9300	C12—H12A	0.9600
C4—C5	1.375 (2)	C12—H12B	0.9600
C4—H4	0.9300	C12—H12C	0.9600
C5—C6	1.3920 (19)

C1—O1—H1	109.5	O3—C8—C9	114.28 (11)
C2—O2—H2	109.5	O3—C8—C7	107.94 (11)
C8—O3—H3	109.5	C9—C8—C7	108.95 (11)
C9—O5—C10	117.99 (11)	O3—C8—H8	108.5
O1—C1—C6	123.19 (12)	C9—C8—H8	108.5
O1—C1—C2	116.83 (13)	C7—C8—H8	108.5
C6—C1—C2	119.97 (13)	O4—C9—O5	124.32 (14)
O2—C2—C3	124.07 (13)	O4—C9—C8	120.62 (14)
O2—C2—C1	117.15 (13)	O5—C9—C8	115.04 (12)
C3—C2—C1	118.78 (14)	O5—C10—C11	106.12 (12)
C2—C3—C4	120.72 (14)	O5—C10—C12	108.65 (14)
C2—C3—H3A	119.6	C11—C10—C12	113.75 (15)
C4—C3—H3A	119.6	O5—C10—H10	109.4
C5—C4—C3	121.15 (15)	C11—C10—H10	109.4
C5—C4—H4	119.4	C12—C10—H10	109.4
C3—C4—H4	119.4	C10—C11—H11A	109.5
C4—C5—C6	117.93 (14)	C10—C11—H11B	109.5
C4—C5—C7	122.71 (14)	H11A—C11—H11B	109.5
C6—C5—C7	119.37 (13)	C10—C11—H11C	109.5
C1—C6—C5	121.41 (13)	H11A—C11—H11C	109.5
C1—C6—H6	119.3	H11B—C11—H11C	109.5
C5—C6—H6	119.3	C10—C12—H12A	109.5
C5—C7—C8	113.23 (11)	C10—C12—H12B	109.5
C5—C7—H7A	108.9	H12A—C12—H12B	109.5
C8—C7—H7A	108.9	C10—C12—H12C	109.5
C5—C7—H7B	108.9	H12A—C12—H12C	109.5
C8—C7—H7B	108.9	H12B—C12—H12C	109.5
H7A—C7—H7B	107.7

O1—C1—C2—O2	2.23 (19)	C4—C5—C7—C8	93.95 (16)
C6—C1—C2—O2	−177.37 (13)	C6—C5—C7—C8	−85.35 (15)
O1—C1—C2—C3	−177.87 (13)	C5—C7—C8—O3	−74.53 (15)
C6—C1—C2—C3	2.5 (2)	C5—C7—C8—C9	160.84 (12)
O2—C2—C3—C4	178.56 (15)	C10—O5—C9—O4	3.3 (2)
C1—C2—C3—C4	−1.3 (2)	C10—O5—C9—C8	−174.98 (12)
C2—C3—C4—C5	−0.4 (2)	O3—C8—C9—O4	167.89 (15)
C3—C4—C5—C6	0.8 (2)	C7—C8—C9—O4	−71.30 (18)
C3—C4—C5—C7	−178.48 (14)	O3—C8—C9—O5	−13.79 (18)
O1—C1—C6—C5	178.33 (12)	C7—C8—C9—O5	107.02 (14)
C2—C1—C6—C5	−2.1 (2)	C9—O5—C10—C11	−156.25 (14)
C4—C5—C6—C1	0.41 (19)	C9—O5—C10—C12	81.06 (17)
C7—C5—C6—C1	179.74 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4ⁱ	0.82	1.96	2.7621 (14)	164
O2—H2···O3ⁱⁱ	0.82	1.93	2.7417 (15)	169
O3—H3···O1ⁱⁱⁱ	0.82	2.00	2.7832 (14)	160

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+5/2, y+1/2, −z+1/2; (iii) −x+3/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₆O₅
M_r	240.25
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	5.7691 (13), 14.271 (3), 14.955 (3)
β (°)	96.360 (3)
V (Å³)	1223.7 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.38 × 0.27 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5934, 2174, 1598
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.106, 1.14
No. of reflections	2174
No. of parameters	159
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.18

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4ⁱ	0.82	1.96	2.7621 (14)	164.4
O2—H2···O3ⁱⁱ	0.82	1.93	2.7417 (15)	169.2
O3—H3···O1ⁱⁱⁱ	0.82	2.00	2.7832 (14)	159.8

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+5/2, y+1/2, −z+1/2; (iii) −x+3/2, y−1/2, −z+1/2.

Acknowledgements

We are grateful for financial support from the Ministry of Education of Shaanxi Province (Nos. 08 J K476, 09 J K702), the National Natural Sciences Foundation of China (No. 20875074) and the West Light Foundation of the Chinese Academy of Sciences (No. 2007DF02).

References

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