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

Abstract

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,

• a = 5.7691 (13) Å

• b = 14.271 (3) Å

• c = 14.955 (3) Å

• β = 96.360 (3)°

• V = 1223.7 (5) ų

• 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[F ² > 2σ(F ²)] = 0.038

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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.

Experimental

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).

Refinement

H atoms bonded to N and O atoms were located in a difference map and refined with distance restraints of O—H = 0.8200 and N—H = 0.8600 Å, and with Uĩso~(H) = 1.2U~eq~(N,O). Other H atoms were positioned geometrically and refined using a riding model (including free rotation about the ethanol C—C bond), with C—H = 0.93–0.96 Å.

Figures

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.

Crystal data

C12H16O5	Dx = 1.304 Mg m−3
Mr = 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

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

Refinement

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(Fo2) + (0.0576P)2] where P = (Fo2 + 2Fc2)/3
2174 reflections	(Δ/σ)max < 0.001
159 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.18 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.