4-(5-Hy­droxy­meth­yl-2-meth­oxy­phen­oxy)benzoic acid

Niu, Y.; Wu, B.

doi:10.1107/S1600536811012190

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1069

doi:10.1107/S1600536811012190

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4-(5-Hydroxymethyl-2-methoxyphenoxy)benzoic acid

Yanyan Niu ^a and Bo Wu ^a ^*

^aSchool of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, People's Republic of China
^*Correspondence e-mail: ny526ny526@gmail.com

(Received 22 March 2011; accepted 1 April 2011; online 7 April 2011)

The title compound, C₁₅H₁₄O₅, crystallizes with two independent molecules in the asymmetric unit in which the benzene rings are inclined at dihedral angles of 79.4 (1) and 84.2 (1)°. In the crystal, intermolecular O—H⋯O hydrogen bonds link the molecules into double chains propagating in [001].

Related literature

For the bioactivity of diphenyl ether derivatives, see: Asakawa (2001 ); Hua et al. (2009 ); Kini et al.(2009 ). For background to Ullman coupling, see: Bringmann et al. (1990 ).

Experimental

Crystal data

C₁₅H₁₄O₅
M_r = 274.26
Triclinic, $[P \overline 1]$
a = 10.5420 (15) Å
b = 10.6153 (15) Å
c = 12.8070 (18) Å
α = 78.024 (2)°
β = 75.184 (2)°
γ = 88.451 (2)°
V = 1354.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 273 K
0.13 × 0.12 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.987, T_max = 0.990
5794 measured reflections
3874 independent reflections
3154 reflections with I > 2σ(I)
R_int = 0.015
θ_max = 23.3°

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.141
S = 1.02
3874 reflections
365 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9⋯O1	0.82	1.80	2.620 (2)	175
O4—H4⋯O6	0.82	1.84	2.652 (2)	170
O6—H6⋯O10ⁱ	0.82	2.01	2.791 (3)	159
O1—H1⋯O5ⁱⁱ	0.82	1.89	2.706 (2)	172
Symmetry codes: (i) x, y, z+1; (ii) x, y, z-1.

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); 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: 10.1107/S1600536811012190/cv5067sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811012190/cv5067Isup2.hkl

checkCIF report

Comment top

The diphenyl ether analogs existing in many natural products exhibit various bioactivities, such as antitubercular (Kini et al., 2009), antibacterial (Hua et al., 2009), and cytotoxic (Asakawa, 2001) activities. Most of the diphenyl ethers were synthesized by Ullman coupling (Bringmann et al., 1990), using Cu complexes as catalysts. Herewith we present the title compound (I) - a new derivative of diphenyl ether.

The asymmetric unit of (I) contains two independent molecules (Fig. 1). In the independent molecules, two benzene rings form the dihedral angles of 79.4 (1) and 84.2 (1)°, respectively. In the crystal structure, O—H···O hydrogen bonds (Table 1) link the molecules into doubled chains propagated in [001].

Related literature top

For the bioactivity of diphenyl ether derivative,s see: Asakawa (2001); Hua et al. (2009); Kini et al.(2009). For background to Ullman coupling, see: Bringmann et al. (1990).

Experimental top

(3-Bromo-4-methoxyphenyl)methanol (5.00 g, 23.04 mmol), and methyl 4-hydroxybenzoate (3.50 g, 23.04 mmol), potassium carbonate (3.17 g, 46.08 mmol), and cupric oxide (0.18 g, 2.25 mmol) in pyridine (20 ml) were added in flask and the mixture was stirred under reflux for 12 h. The pyridine was distilled in vacuo and the residue was extracted with CH₂Cl₂(3*30 ml). The solution was concentrated and the residue was purified by flash column chromatograph on Al₂O₃, The yield of the coupling product was 4.35 g (65%) as white solid. The coupling products was hydrolyzed with 20% NaOH aq and then acidified to pH=6.0 with 1M HCl. The final product was extracted with CH₂Cl₂ (3*20 ml) and obtained the white solid by vacuum distillation. (4.11 g, 99%). The colourless crystals suitable for an X-ray diffraction experiment were obtained by cystal growth from ethanol.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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. Two independent molecules of (I) showing the atomic numbering and 50% probabilty displacement ellipsoids.

4-(5-Hydroxymethyl-2-methoxyphenoxy)benzoic acid top

Crystal data top

C₁₅H₁₄O₅	Z = 4
M_r = 274.26	F(000) = 576
Triclinic, P1	D_x = 1.345 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.5420 (15) Å	Cell parameters from 2550 reflections
b = 10.6153 (15) Å	θ = 2.8–23.3°
c = 12.8070 (18) Å	µ = 0.10 mm⁻¹
α = 78.024 (2)°	T = 273 K
β = 75.184 (2)°	Block, colourless
γ = 88.451 (2)°	0.13 × 0.12 × 0.10 mm
V = 1354.9 (3) Å³

Data collection top

Bruker APEXII CCD diffractometer	3874 independent reflections
Radiation source: fine-focus sealed tube	3154 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
phi and ω scans	θ_max = 23.3°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −11→11
T_min = 0.987, T_max = 0.990	k = −11→5
5794 measured reflections	l = −14→13

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) = 0.141	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.093P)² + 0.1798P] where P = (F_o² + 2F_c²)/3
3874 reflections	(Δ/σ)_max < 0.001
365 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₅H₁₄O₅	γ = 88.451 (2)°
M_r = 274.26	V = 1354.9 (3) Å³
Triclinic, P1	Z = 4
a = 10.5420 (15) Å	Mo Kα radiation
b = 10.6153 (15) Å	µ = 0.10 mm⁻¹
c = 12.8070 (18) Å	T = 273 K
α = 78.024 (2)°	0.13 × 0.12 × 0.10 mm
β = 75.184 (2)°

Data collection top

Bruker APEXII CCD diffractometer	3874 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	3154 reflections with I > 2σ(I)
T_min = 0.987, T_max = 0.990	R_int = 0.015
5794 measured reflections	θ_max = 23.3°

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.141	H-atom parameters constrained
S = 1.02	Δρ_max = 0.22 e Å⁻³
3874 reflections	Δρ_min = −0.19 e Å⁻³
365 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
O8	0.45863 (12)	0.12659 (13)	0.65556 (10)	0.0507 (4)
O7	0.68968 (14)	0.00872 (15)	0.63970 (12)	0.0595 (4)
C22	0.52664 (18)	0.12698 (18)	0.73608 (16)	0.0447 (5)
C16	0.51038 (17)	0.20109 (18)	0.55175 (15)	0.0424 (5)
C19	0.60706 (19)	0.33828 (19)	0.33809 (16)	0.0480 (5)
C20	0.5219 (2)	0.2327 (2)	0.35983 (17)	0.0500 (5)
H20A	0.4978	0.2079	0.3019	0.060*
C23	0.64416 (19)	0.06201 (18)	0.73023 (16)	0.0470 (5)
C21	0.47319 (19)	0.16482 (19)	0.46587 (16)	0.0475 (5)
H21A	0.4156	0.0949	0.4799	0.057*
C27	0.4736 (2)	0.1865 (2)	0.82238 (16)	0.0510 (5)
H27A	0.3956	0.2301	0.8245	0.061*
C24	0.7062 (2)	0.0578 (2)	0.81386 (18)	0.0566 (6)
H24A	0.7845	0.0148	0.8119	0.068*
C17	0.5919 (2)	0.30742 (19)	0.53229 (17)	0.0511 (5)
H17A	0.6142	0.3332	0.5905	0.061*
O10	0.6491 (2)	0.36489 (19)	0.14387 (14)	0.0957 (7)
O9	0.7344 (2)	0.50767 (18)	0.21132 (13)	0.0866 (6)
H9	0.7690	0.5355	0.1457	0.130*
C18	0.6399 (2)	0.3752 (2)	0.42520 (16)	0.0520 (5)
H18A	0.6952	0.4469	0.4116	0.062*
C26	0.5356 (2)	0.1820 (2)	0.90646 (16)	0.0543 (5)
C25	0.6514 (2)	0.1177 (2)	0.90050 (18)	0.0605 (6)
H25A	0.6940	0.1144	0.9562	0.073*
C28	0.6631 (2)	0.4042 (2)	0.22227 (18)	0.0590 (6)
C29	0.8069 (3)	−0.0626 (3)	0.6332 (2)	0.0796 (8)
H29A	0.8279	−0.0952	0.5665	0.119*
H29B	0.7942	−0.1332	0.6957	0.119*
H29C	0.8776	−0.0074	0.6331	0.119*
O3	1.04180 (13)	0.76114 (15)	0.31213 (12)	0.0619 (4)
C7	0.9680 (2)	0.70611 (19)	0.41650 (17)	0.0502 (5)
O2	0.89962 (16)	0.97320 (16)	0.31548 (14)	0.0700 (5)
O5	0.8207 (2)	0.5321 (2)	0.82261 (14)	0.0896 (6)
C1	0.97799 (19)	0.8027 (2)	0.22881 (17)	0.0516 (5)
C12	0.8381 (2)	0.66884 (19)	0.43978 (17)	0.0501 (5)
H12A	0.7941	0.6824	0.3842	0.060*
C10	0.8387 (2)	0.59194 (19)	0.63005 (17)	0.0524 (5)
C11	0.7735 (2)	0.61085 (19)	0.54690 (17)	0.0503 (5)
H11A	0.6860	0.5844	0.5632	0.060*
C3	0.9363 (2)	0.7804 (2)	0.05822 (17)	0.0560 (6)
C6	0.90656 (19)	0.9154 (2)	0.22828 (17)	0.0517 (5)
C2	0.9932 (2)	0.7374 (2)	0.14517 (18)	0.0561 (5)
H2A	1.0423	0.6632	0.1466	0.067*
O4	0.65453 (19)	0.48294 (19)	0.75911 (13)	0.0810 (5)
H4	0.6192	0.4596	0.8251	0.122*
C8	1.0346 (2)	0.6871 (2)	0.4979 (2)	0.0612 (6)
H8A	1.1225	0.7124	0.4811	0.073*
C15	0.7709 (3)	0.5337 (2)	0.74642 (18)	0.0630 (6)
C5	0.8493 (2)	0.9587 (2)	0.14235 (19)	0.0589 (6)
H5A	0.8006	1.0331	0.1406	0.071*
C9	0.9694 (2)	0.6303 (2)	0.60459 (19)	0.0616 (6)
H9A	1.0137	0.6177	0.6599	0.074*
C4	0.8646 (2)	0.8908 (2)	0.05883 (18)	0.0603 (6)
H4A	0.8254	0.9206	0.0014	0.072*
C14	0.9473 (3)	0.7054 (3)	−0.03082 (19)	0.0724 (7)
H14A	0.9394	0.7625	−0.0984	0.087*
H14B	1.0321	0.6655	−0.0453	0.087*
C13	0.8180 (3)	1.0823 (2)	0.3227 (2)	0.0787 (7)
H13A	0.8209	1.1140	0.3870	0.118*
H13B	0.7294	1.0575	0.3279	0.118*
H13C	0.8490	1.1487	0.2580	0.118*
O6	0.5358 (2)	0.37953 (16)	0.96729 (14)	0.0863 (6)
H6	0.5827	0.3883	1.0075	0.129*
O1	0.8463 (2)	0.6102 (2)	0.00454 (13)	0.0946 (7)
H1	0.8407	0.5796	−0.0479	0.142*
C30	0.4822 (3)	0.2530 (3)	0.99757 (19)	0.0717 (7)
H30A	0.3874	0.2556	1.0121	0.086*
H30B	0.5041	0.2083	1.0646	0.086*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O8	0.0490 (8)	0.0603 (9)	0.0454 (8)	−0.0110 (6)	−0.0185 (6)	−0.0068 (7)
O7	0.0618 (9)	0.0643 (9)	0.0656 (10)	0.0097 (7)	−0.0272 (7)	−0.0302 (8)
C22	0.0472 (11)	0.0465 (11)	0.0426 (11)	−0.0110 (9)	−0.0170 (9)	−0.0060 (9)
C16	0.0414 (10)	0.0445 (11)	0.0446 (11)	0.0036 (8)	−0.0165 (8)	−0.0102 (9)
C19	0.0531 (11)	0.0491 (11)	0.0458 (11)	0.0032 (9)	−0.0194 (9)	−0.0108 (9)
C20	0.0585 (12)	0.0534 (12)	0.0479 (12)	−0.0010 (10)	−0.0275 (10)	−0.0148 (10)
C23	0.0549 (12)	0.0412 (11)	0.0484 (12)	−0.0052 (9)	−0.0197 (9)	−0.0082 (9)
C21	0.0477 (11)	0.0470 (11)	0.0546 (13)	−0.0028 (9)	−0.0240 (9)	−0.0119 (10)
C27	0.0496 (11)	0.0546 (12)	0.0478 (12)	−0.0043 (9)	−0.0104 (9)	−0.0102 (10)
C24	0.0651 (13)	0.0525 (12)	0.0597 (13)	0.0017 (10)	−0.0315 (11)	−0.0090 (10)
C17	0.0613 (12)	0.0504 (12)	0.0479 (12)	−0.0092 (10)	−0.0214 (10)	−0.0136 (9)
O10	0.1400 (18)	0.1021 (15)	0.0491 (10)	−0.0394 (13)	−0.0320 (10)	−0.0091 (10)
O9	0.1231 (15)	0.0779 (12)	0.0519 (10)	−0.0380 (11)	−0.0120 (10)	−0.0062 (9)
C18	0.0616 (13)	0.0464 (11)	0.0518 (13)	−0.0090 (10)	−0.0193 (10)	−0.0111 (10)
C26	0.0656 (14)	0.0556 (13)	0.0401 (11)	−0.0127 (11)	−0.0113 (10)	−0.0075 (9)
C25	0.0786 (16)	0.0599 (14)	0.0505 (13)	−0.0066 (12)	−0.0334 (11)	−0.0063 (10)
C28	0.0713 (14)	0.0584 (14)	0.0496 (13)	−0.0051 (11)	−0.0208 (11)	−0.0089 (11)
C29	0.0760 (16)	0.0827 (18)	0.099 (2)	0.0262 (14)	−0.0367 (15)	−0.0474 (16)
O3	0.0482 (8)	0.0761 (10)	0.0612 (10)	0.0049 (7)	−0.0208 (7)	−0.0056 (8)
C7	0.0533 (12)	0.0481 (12)	0.0552 (13)	0.0113 (9)	−0.0229 (10)	−0.0143 (10)
O2	0.0745 (10)	0.0656 (10)	0.0815 (11)	0.0104 (8)	−0.0311 (9)	−0.0285 (9)
O5	0.1208 (15)	0.1074 (15)	0.0559 (10)	0.0156 (12)	−0.0428 (11)	−0.0273 (10)
C1	0.0435 (11)	0.0556 (13)	0.0555 (13)	−0.0004 (9)	−0.0175 (9)	−0.0046 (10)
C12	0.0549 (12)	0.0488 (11)	0.0534 (12)	0.0040 (9)	−0.0265 (10)	−0.0103 (10)
C10	0.0704 (14)	0.0436 (11)	0.0539 (13)	0.0145 (10)	−0.0288 (11)	−0.0196 (9)
C11	0.0600 (12)	0.0445 (11)	0.0537 (13)	0.0056 (9)	−0.0246 (10)	−0.0141 (10)
C3	0.0550 (12)	0.0602 (14)	0.0467 (12)	−0.0099 (10)	−0.0066 (10)	−0.0038 (10)
C6	0.0452 (11)	0.0513 (12)	0.0570 (13)	−0.0050 (9)	−0.0114 (9)	−0.0085 (10)
C2	0.0527 (12)	0.0523 (12)	0.0594 (14)	0.0043 (10)	−0.0105 (10)	−0.0084 (11)
O4	0.1012 (14)	0.0868 (13)	0.0534 (10)	−0.0133 (11)	−0.0265 (9)	−0.0004 (9)
C8	0.0554 (13)	0.0679 (14)	0.0722 (16)	0.0094 (11)	−0.0329 (12)	−0.0211 (12)
C15	0.0921 (18)	0.0545 (13)	0.0526 (14)	0.0174 (13)	−0.0313 (13)	−0.0201 (11)
C5	0.0561 (13)	0.0518 (13)	0.0648 (14)	0.0032 (10)	−0.0176 (11)	−0.0007 (11)
C9	0.0741 (15)	0.0658 (14)	0.0603 (15)	0.0166 (12)	−0.0390 (12)	−0.0221 (12)
C4	0.0563 (13)	0.0685 (15)	0.0512 (13)	−0.0053 (11)	−0.0170 (10)	0.0033 (11)
C14	0.0780 (16)	0.0839 (18)	0.0500 (13)	−0.0120 (14)	−0.0063 (11)	−0.0131 (12)
C13	0.0876 (18)	0.0606 (15)	0.0837 (18)	0.0078 (13)	−0.0080 (14)	−0.0234 (13)
O6	0.1443 (18)	0.0613 (11)	0.0554 (10)	−0.0033 (11)	−0.0256 (10)	−0.0161 (8)
O1	0.1292 (16)	0.1022 (15)	0.0485 (10)	−0.0476 (13)	−0.0084 (10)	−0.0180 (10)
C30	0.0852 (17)	0.0803 (17)	0.0516 (14)	−0.0086 (13)	−0.0136 (12)	−0.0216 (12)

Geometric parameters (Å, º) top

O8—C16	1.381 (2)	O2—C6	1.367 (3)
O8—C22	1.399 (2)	O2—C13	1.428 (3)
O7—C23	1.367 (2)	O5—C15	1.218 (3)
O7—C29	1.425 (3)	C1—C2	1.367 (3)
C22—C27	1.374 (3)	C1—C6	1.396 (3)
C22—C23	1.394 (3)	C12—C11	1.385 (3)
C16—C17	1.378 (3)	C12—H12A	0.9300
C16—C21	1.384 (3)	C10—C9	1.384 (3)
C19—C18	1.380 (3)	C10—C11	1.388 (3)
C19—C20	1.392 (3)	C10—C15	1.487 (3)
C19—C28	1.477 (3)	C11—H11A	0.9300
C20—C21	1.373 (3)	C3—C4	1.377 (3)
C20—H20A	0.9300	C3—C2	1.387 (3)
C23—C24	1.383 (3)	C3—C14	1.500 (3)
C21—H21A	0.9300	C6—C5	1.379 (3)
C27—C26	1.387 (3)	C2—H2A	0.9300
C27—H27A	0.9300	O4—C15	1.311 (3)
C24—C25	1.384 (3)	O4—H4	0.8200
C24—H24A	0.9300	C8—C9	1.379 (3)
C17—C18	1.382 (3)	C8—H8A	0.9300
C17—H17A	0.9300	C5—C4	1.384 (3)
O10—C28	1.207 (3)	C5—H5A	0.9300
O9—C28	1.311 (3)	C9—H9A	0.9300
O9—H9	0.8200	C4—H4A	0.9300
C18—H18A	0.9300	C14—O1	1.408 (3)
C26—C25	1.375 (3)	C14—H14A	0.9700
C26—C30	1.501 (3)	C14—H14B	0.9700
C25—H25A	0.9300	C13—H13A	0.9600
C29—H29A	0.9600	C13—H13B	0.9600
C29—H29B	0.9600	C13—H13C	0.9600
C29—H29C	0.9600	O6—C30	1.409 (3)
O3—C7	1.379 (3)	O6—H6	0.8200
O3—C1	1.393 (2)	O1—H1	0.8200
C7—C12	1.376 (3)	C30—H30A	0.9700
C7—C8	1.378 (3)	C30—H30B	0.9700

C16—O8—C22	117.53 (13)	O3—C1—C6	119.31 (19)
C23—O7—C29	117.67 (17)	C7—C12—C11	119.26 (18)
C27—C22—C23	121.00 (18)	C7—C12—H12A	120.4
C27—C22—O8	119.45 (18)	C11—C12—H12A	120.4
C23—C22—O8	119.49 (17)	C9—C10—C11	119.3 (2)
C17—C16—O8	123.43 (17)	C9—C10—C15	119.11 (19)
C17—C16—C21	120.64 (18)	C11—C10—C15	121.6 (2)
O8—C16—C21	115.91 (16)	C12—C11—C10	120.4 (2)
C18—C19—C20	118.90 (18)	C12—C11—H11A	119.8
C18—C19—C28	122.14 (18)	C10—C11—H11A	119.8
C20—C19—C28	118.92 (18)	C4—C3—C2	117.9 (2)
C21—C20—C19	120.65 (18)	C4—C3—C14	121.1 (2)
C21—C20—H20A	119.7	C2—C3—C14	120.9 (2)
C19—C20—H20A	119.7	O2—C6—C5	125.7 (2)
O7—C23—C24	125.23 (19)	O2—C6—C1	115.72 (19)
O7—C23—C22	116.22 (16)	C5—C6—C1	118.6 (2)
C24—C23—C22	118.54 (19)	C1—C2—C3	120.8 (2)
C20—C21—C16	119.57 (18)	C1—C2—H2A	119.6
C20—C21—H21A	120.2	C3—C2—H2A	119.6
C16—C21—H21A	120.2	C15—O4—H4	109.5
C22—C27—C26	120.5 (2)	C7—C8—C9	119.3 (2)
C22—C27—H27A	119.7	C7—C8—H8A	120.3
C26—C27—H27A	119.7	C9—C8—H8A	120.3
C23—C24—C25	119.8 (2)	O5—C15—O4	123.3 (2)
C23—C24—H24A	120.1	O5—C15—C10	122.5 (2)
C25—C24—H24A	120.1	O4—C15—C10	114.19 (19)
C16—C17—C18	119.21 (18)	C6—C5—C4	119.6 (2)
C16—C17—H17A	120.4	C6—C5—H5A	120.2
C18—C17—H17A	120.4	C4—C5—H5A	120.2
C28—O9—H9	109.5	C8—C9—C10	120.6 (2)
C19—C18—C17	120.98 (18)	C8—C9—H9A	119.7
C19—C18—H18A	119.5	C10—C9—H9A	119.7
C17—C18—H18A	119.5	C3—C4—C5	122.0 (2)
C25—C26—C27	118.34 (19)	C3—C4—H4A	119.0
C25—C26—C30	120.8 (2)	C5—C4—H4A	119.0
C27—C26—C30	120.7 (2)	O1—C14—C3	108.56 (18)
C26—C25—C24	121.80 (19)	O1—C14—H14A	110.0
C26—C25—H25A	119.1	C3—C14—H14A	110.0
C24—C25—H25A	119.1	O1—C14—H14B	110.0
O10—C28—O9	122.3 (2)	C3—C14—H14B	110.0
O10—C28—C19	123.6 (2)	H14A—C14—H14B	108.4
O9—C28—C19	113.99 (19)	O2—C13—H13A	109.5
O7—C29—H29A	109.5	O2—C13—H13B	109.5
O7—C29—H29B	109.5	H13A—C13—H13B	109.5
H29A—C29—H29B	109.5	O2—C13—H13C	109.5
O7—C29—H29C	109.5	H13A—C13—H13C	109.5
H29A—C29—H29C	109.5	H13B—C13—H13C	109.5
H29B—C29—H29C	109.5	C30—O6—H6	109.5
C7—O3—C1	118.79 (15)	C14—O1—H1	109.5
C12—C7—C8	121.1 (2)	O6—C30—C26	109.97 (19)
C12—C7—O3	123.66 (18)	O6—C30—H30A	109.7
C8—C7—O3	115.18 (19)	C26—C30—H30A	109.7
C6—O2—C13	117.22 (18)	O6—C30—H30B	109.7
C2—C1—O3	119.55 (19)	C26—C30—H30B	109.7
C2—C1—C6	121.01 (19)	H30A—C30—H30B	108.2

C16—O8—C22—C27	109.7 (2)	C7—O3—C1—C2	−109.8 (2)
C16—O8—C22—C23	−73.2 (2)	C7—O3—C1—C6	74.4 (2)
C22—O8—C16—C17	−24.5 (3)	C8—C7—C12—C11	−0.2 (3)
C22—O8—C16—C21	156.97 (17)	O3—C7—C12—C11	178.08 (18)
C18—C19—C20—C21	−1.2 (3)	C7—C12—C11—C10	0.8 (3)
C28—C19—C20—C21	176.59 (19)	C9—C10—C11—C12	−0.7 (3)
C29—O7—C23—C24	3.4 (3)	C15—C10—C11—C12	178.07 (18)
C29—O7—C23—C22	−177.65 (19)	C13—O2—C6—C5	5.0 (3)
C27—C22—C23—O7	−178.58 (17)	C13—O2—C6—C1	−174.72 (19)
O8—C22—C23—O7	4.4 (3)	C2—C1—C6—O2	−179.12 (18)
C27—C22—C23—C24	0.5 (3)	O3—C1—C6—O2	−3.4 (3)
O8—C22—C23—C24	−176.58 (17)	C2—C1—C6—C5	1.1 (3)
C19—C20—C21—C16	−0.7 (3)	O3—C1—C6—C5	176.89 (18)
C17—C16—C21—C20	2.4 (3)	O3—C1—C2—C3	−176.70 (18)
O8—C16—C21—C20	−179.01 (16)	C6—C1—C2—C3	−1.0 (3)
C23—C22—C27—C26	−0.7 (3)	C4—C3—C2—C1	0.2 (3)
O8—C22—C27—C26	176.39 (17)	C14—C3—C2—C1	−177.01 (18)
O7—C23—C24—C25	178.76 (19)	C12—C7—C8—C9	−0.3 (3)
C22—C23—C24—C25	−0.2 (3)	O3—C7—C8—C9	−178.76 (19)
O8—C16—C17—C18	179.35 (18)	C9—C10—C15—O5	8.9 (3)
C21—C16—C17—C18	−2.2 (3)	C11—C10—C15—O5	−169.9 (2)
C20—C19—C18—C17	1.4 (3)	C9—C10—C15—O4	−170.1 (2)
C28—C19—C18—C17	−176.28 (19)	C11—C10—C15—O4	11.1 (3)
C16—C17—C18—C19	0.2 (3)	O2—C6—C5—C4	179.73 (18)
C22—C27—C26—C25	0.6 (3)	C1—C6—C5—C4	−0.6 (3)
C22—C27—C26—C30	176.53 (19)	C7—C8—C9—C10	0.3 (3)
C27—C26—C25—C24	−0.3 (3)	C11—C10—C9—C8	0.2 (3)
C30—C26—C25—C24	−176.3 (2)	C15—C10—C9—C8	−178.65 (19)
C23—C24—C25—C26	0.1 (3)	C2—C3—C4—C5	0.4 (3)
C18—C19—C28—O10	170.7 (2)	C14—C3—C4—C5	177.58 (19)
C20—C19—C28—O10	−7.0 (4)	C6—C5—C4—C3	−0.2 (3)
C18—C19—C28—O9	−6.9 (3)	C4—C3—C14—O1	−91.9 (3)
C20—C19—C28—O9	175.4 (2)	C2—C3—C14—O1	85.2 (3)
C1—O3—C7—C12	11.8 (3)	C25—C26—C30—O6	87.2 (3)
C1—O3—C7—C8	−169.74 (19)	C27—C26—C30—O6	−88.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9···O1	0.82	1.80	2.620 (2)	175
O4—H4···O6	0.82	1.84	2.652 (2)	170
O6—H6···O10ⁱ	0.82	2.01	2.791 (3)	159
O1—H1···O5ⁱⁱ	0.82	1.89	2.706 (2)	172

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₄O₅
M_r	274.26
Crystal system, space group	Triclinic, P1
Temperature (K)	273
a, b, c (Å)	10.5420 (15), 10.6153 (15), 12.8070 (18)
α, β, γ (°)	78.024 (2), 75.184 (2), 88.451 (2)
V (Å³)	1354.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.13 × 0.12 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.987, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	5794, 3874, 3154
R_int	0.015
θ_max (°)	23.3
(sin θ/λ)_max (Å⁻¹)	0.557

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.141, 1.02
No. of reflections	3874
No. of parameters	365
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.19

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), 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
O9—H9···O1	0.82	1.80	2.620 (2)	175
O4—H4···O6	0.82	1.84	2.652 (2)	170
O6—H6···O10ⁱ	0.82	2.01	2.791 (3)	159
O1—H1···O5ⁱⁱ	0.82	1.89	2.706 (2)	172

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

Acknowledgements

Financial support from the Department of Science and Technology of Shandong Province is gratefully acknowledged.

References

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