2,2′-[4-Acetyl-1,3-phenyl­enebis(­oxy)]diacetic acid

Wang, J.-G.; Yan, P.; Zhong, C.; Yu, G.

doi:10.1107/S1600536812047897

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3470

doi:10.1107/S1600536812047897

Open

access

2,2′-[4-Acetyl-1,3-phenylenebis(oxy)]diacetic acid

Jian-Guo Wang,^a ^* Ping Yan,^a Chan-juan Zhong ^a and Guo-zhen Yu ^a

^aSchool of Chemistry & Environmental Engineering, Jiujiang University, Jiujiang 332005, People's Republic of China
^*Correspondence e-mail: jgwang117@163.com

(Received 9 November 2012; accepted 21 November 2012; online 28 November 2012)

In the title compound, C₁₂H₁₂O₇, the dihedral angles between the benzene ring and the mean planes of the 3-carboxymethoxy, 1-carboxymethoxy and acetyl substituents are 8.67 (7), 7.81 (6) and 10.3 (18)°, respectively. In the crystal, molecules are linked by typical carboxylic acid O—H⋯O hydrogen bonds, forming a zigzag chain. C—H⋯O interactions also occur.

Related literature

For a related structure, see: Zhang et al. (2007 ).

Experimental

Crystal data

C₁₂H₁₂O₇
M_r = 268.22
Triclinic, $[P \overline 1]$
a = 5.1351 (6) Å
b = 7.8346 (9) Å
c = 15.6157 (18) Å
α = 86.217 (2)°
β = 81.321 (1)°
γ = 72.101 (2)°
V = 590.86 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 298 K
0.12 × 0.10 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.985, T_max = 0.987
3902 measured reflections
2049 independent reflections
1860 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.120
S = 1.05
2049 reflections
176 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.82	1.83	2.6530 (14)	180
O6—H6⋯O5ⁱⁱ	0.82	1.83	2.6352 (15)	167
C2—H2⋯O7ⁱⁱⁱ	0.93	2.44	3.3566 (17)	168
C4—H4⋯O6^iv	0.93	2.52	3.4392 (19)	169
Symmetry codes: (i) -x+3, -y+2, -z; (ii) -x-1, -y+2, -z+1; (iii) x-1, y+1, z; (iv) -x, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812047897/go2075sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812047897/go2075Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812047897/go2075Isup3.cml

checkCIF report

Comment top

The title compound is a potential inhibitor of mushroom tyrosinase.

The dihedral angles between the mean planes of the benzene ring and those of the 2-carboxymethoxyl,(O1-C8-C7-O3-O2), 4-carboxymethoxyl (O6-C10-C9-O4-O5), and acetyl, (C11-C12-O7), substituents are 8.67 (7)°, 7.81 (6)°, and 10.3 (18)° respectively.

In the crystal, the molecules are linked by typical carboxylic acid O—H···O hydrogen bonding forming a one-dimensional zig-zag chain Table 1, Figure 2.

This chain is linked to anti-parallel chains by C—H···O weak hydrogen bonds to form a two dimensional sheet stabilizing the supramolecular structure, Table 1, Figure 2.

Related literature top

For a related structure, see: Zhang et al. (2007).

Experimental top

2,4-dihydroxyacetophenone (10.64 g, 0.07 mol) and potassium hydroxide (10.58 g, 0.189 mol) were dissolved in dry acetone (100 ml) in a three-neck flask. Then ethyl bromoacetate (28.06 g, 0.168 mol) was dropwise added at room temperature and vigorously stirred for 3 h. The progress of the reaction was monitored by TCL (Si gel, developing solvent V (acetone) /V (petroleum ether) = 1:2). After suction filtration and distillation to remove the solvent, a white solid was obtained, 19.76 g, yield 87.1%. This solid was dissolved in acetone (30 ml) and 20% aq. NaOH (50 ml) was added. The reaction mixture was stirred at 323 K for 1.5 h. After acidifying the misxture with dilute hydrochloric acid to pH=3, followed by suction filtrationand washing the residue with water, the target product was prepared. After recrystallization from ethanol, crystalline colorless needles were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal packing for (I), with hydrogen bonds shown as dashed lines. Hydrogen atoms not involved in the hydrogen bonding have been omitted.

2,2'-[4-Acetyl-1,3-phenylenebis(oxy)]diacetic acid top

Crystal data top

C₁₂H₁₂O₇	Z = 2
M_r = 268.22	F(000) = 280
Triclinic, P1	D_x = 1.508 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.1351 (6) Å	Cell parameters from 3359 reflections
b = 7.8346 (9) Å	θ = 2.6–31.8°
c = 15.6157 (18) Å	µ = 0.13 mm⁻¹
α = 86.217 (2)°	T = 298 K
β = 81.321 (1)°	Block, colourless
γ = 72.101 (2)°	0.12 × 0.10 × 0.10 mm
V = 590.86 (12) Å³

Data collection top

Bruker APEXII CCD diffractometer	2049 independent reflections
Radiation source: fine-focus sealed tube	1860 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −6→6
T_min = 0.985, T_max = 0.987	k = −9→9
3902 measured reflections	l = −18→18

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.120	w = 1/[σ²(F_o²) + (0.0795P)² + 0.1078P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2049 reflections	Δρ_max = 0.24 e Å⁻³
176 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.036 (8)

Crystal data top

C₁₂H₁₂O₇	γ = 72.101 (2)°
M_r = 268.22	V = 590.86 (12) Å³
Triclinic, P1	Z = 2
a = 5.1351 (6) Å	Mo Kα radiation
b = 7.8346 (9) Å	µ = 0.13 mm⁻¹
c = 15.6157 (18) Å	T = 298 K
α = 86.217 (2)°	0.12 × 0.10 × 0.10 mm
β = 81.321 (1)°

Data collection top

Bruker APEXII CCD diffractometer	2049 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1860 reflections with I > 2σ(I)
T_min = 0.985, T_max = 0.987	R_int = 0.016
3902 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.05	Δρ_max = 0.24 e Å⁻³
2049 reflections	Δρ_min = −0.23 e Å⁻³
176 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
C1	0.9386 (3)	0.64900 (17)	0.22991 (8)	0.0282 (3)
C2	0.6877 (3)	0.75023 (17)	0.27294 (9)	0.0291 (3)
H2	0.6254	0.8735	0.2630	0.035*
C3	0.5297 (3)	0.66705 (18)	0.33088 (9)	0.0290 (3)
C4	0.6221 (3)	0.48246 (18)	0.34697 (9)	0.0332 (3)
H4	0.5166	0.4266	0.3858	0.040*
C5	0.8736 (3)	0.38464 (17)	0.30388 (9)	0.0329 (3)
H5	0.9361	0.2618	0.3152	0.040*
C6	1.0383 (3)	0.46109 (17)	0.24430 (9)	0.0299 (3)
C7	1.0249 (3)	0.90973 (18)	0.15901 (10)	0.0349 (3)
H7A	1.0211	0.9696	0.2118	0.042*
H7B	0.8424	0.9519	0.1412	0.042*
C8	1.2360 (3)	0.94824 (18)	0.08886 (9)	0.0329 (3)
C9	0.1228 (3)	0.70250 (18)	0.43152 (9)	0.0323 (3)
H9A	0.2214	0.6572	0.4806	0.039*
H9B	0.0869	0.6029	0.4068	0.039*
C10	−0.1449 (3)	0.84177 (18)	0.46089 (9)	0.0321 (3)
C11	1.3024 (3)	0.33765 (19)	0.20074 (10)	0.0363 (3)
C12	1.4694 (4)	0.3989 (2)	0.12491 (12)	0.0524 (5)
H12A	1.6153	0.2977	0.1007	0.079*
H12B	1.5473	0.4845	0.1436	0.079*
H12C	1.3527	0.4537	0.0818	0.079*
O1	1.1504 (2)	1.10815 (14)	0.05426 (8)	0.0472 (3)
H1	1.2707	1.1235	0.0164	0.071*
O2	1.4614 (2)	0.84065 (14)	0.06836 (7)	0.0463 (3)
O3	1.1036 (2)	0.72247 (13)	0.17277 (7)	0.0406 (3)
O4	0.28549 (19)	0.77925 (13)	0.36867 (7)	0.0369 (3)
O5	−0.2075 (2)	0.99593 (13)	0.43053 (7)	0.0421 (3)
O6	−0.2994 (2)	0.78060 (14)	0.51955 (8)	0.0487 (3)
H6	−0.4400	0.8616	0.5357	0.073*
O7	1.3789 (3)	0.18327 (14)	0.22649 (9)	0.0579 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0251 (6)	0.0269 (6)	0.0304 (6)	−0.0088 (5)	0.0037 (5)	0.0021 (5)
C2	0.0258 (7)	0.0232 (6)	0.0344 (7)	−0.0059 (5)	0.0025 (5)	0.0039 (5)
C3	0.0231 (6)	0.0288 (7)	0.0317 (7)	−0.0059 (5)	0.0019 (5)	0.0009 (5)
C4	0.0300 (7)	0.0300 (7)	0.0372 (7)	−0.0111 (5)	0.0041 (6)	0.0061 (5)
C5	0.0315 (7)	0.0233 (6)	0.0408 (8)	−0.0071 (5)	0.0005 (6)	0.0034 (5)
C6	0.0279 (7)	0.0247 (7)	0.0344 (7)	−0.0065 (6)	0.0003 (5)	−0.0003 (5)
C7	0.0299 (7)	0.0264 (7)	0.0420 (8)	−0.0064 (5)	0.0089 (6)	0.0039 (6)
C8	0.0306 (7)	0.0283 (7)	0.0375 (7)	−0.0101 (6)	0.0031 (6)	0.0028 (5)
C9	0.0266 (7)	0.0322 (7)	0.0342 (7)	−0.0087 (6)	0.0057 (5)	0.0036 (6)
C10	0.0292 (7)	0.0322 (7)	0.0328 (7)	−0.0105 (6)	0.0051 (5)	−0.0010 (5)
C11	0.0314 (7)	0.0283 (7)	0.0448 (8)	−0.0061 (6)	0.0033 (6)	−0.0045 (6)
C12	0.0432 (9)	0.0373 (8)	0.0602 (10)	−0.0011 (7)	0.0226 (8)	−0.0061 (7)
O1	0.0391 (6)	0.0365 (6)	0.0568 (7)	−0.0098 (5)	0.0118 (5)	0.0142 (5)
O2	0.0342 (6)	0.0394 (6)	0.0540 (7)	−0.0066 (5)	0.0142 (5)	0.0094 (5)
O3	0.0337 (6)	0.0259 (5)	0.0518 (6)	−0.0064 (4)	0.0185 (4)	0.0047 (4)
O4	0.0270 (5)	0.0298 (5)	0.0446 (6)	−0.0047 (4)	0.0126 (4)	0.0052 (4)
O5	0.0344 (6)	0.0333 (6)	0.0508 (6)	−0.0076 (4)	0.0102 (5)	0.0047 (4)
O6	0.0371 (6)	0.0384 (6)	0.0574 (7)	−0.0071 (5)	0.0228 (5)	0.0052 (5)
O7	0.0491 (7)	0.0285 (6)	0.0774 (9)	0.0037 (5)	0.0135 (6)	0.0050 (5)

Geometric parameters (Å, º) top

C1—O3	1.3596 (16)	C8—O2	1.2154 (18)
C1—C2	1.3862 (19)	C8—O1	1.3033 (17)
C1—C6	1.4170 (18)	C9—O4	1.4166 (15)
C2—C3	1.3884 (18)	C9—C10	1.4979 (19)
C2—H2	0.9300	C9—H9A	0.9700
C3—O4	1.3642 (17)	C9—H9B	0.9700
C3—C4	1.3949 (19)	C10—O5	1.2323 (17)
C4—C5	1.381 (2)	C10—O6	1.2863 (17)
C4—H4	0.9300	C11—O7	1.2126 (18)
C5—C6	1.3927 (19)	C11—C12	1.496 (2)
C5—H5	0.9300	C12—H12A	0.9600
C6—C11	1.4966 (19)	C12—H12B	0.9600
C7—O3	1.4079 (16)	C12—H12C	0.9600
C7—C8	1.5050 (18)	O1—H1	0.8200
C7—H7A	0.9700	O6—H6	0.8200
C7—H7B	0.9700

O3—C1—C2	122.68 (11)	O2—C8—C7	122.72 (12)
O3—C1—C6	116.25 (11)	O1—C8—C7	112.58 (12)
C2—C1—C6	121.06 (12)	O4—C9—C10	109.47 (11)
C1—C2—C3	119.83 (11)	O4—C9—H9A	109.8
C1—C2—H2	120.1	C10—C9—H9A	109.8
C3—C2—H2	120.1	O4—C9—H9B	109.8
O4—C3—C2	114.79 (11)	C10—C9—H9B	109.8
O4—C3—C4	124.56 (12)	H9A—C9—H9B	108.2
C2—C3—C4	120.65 (12)	O5—C10—O6	124.81 (13)
C5—C4—C3	118.49 (12)	O5—C10—C9	122.91 (12)
C5—C4—H4	120.8	O6—C10—C9	112.28 (11)
C3—C4—H4	120.8	O7—C11—C12	119.44 (13)
C4—C5—C6	123.14 (12)	O7—C11—C6	118.94 (13)
C4—C5—H5	118.4	C12—C11—C6	121.60 (12)
C6—C5—H5	118.4	C11—C12—H12A	109.5
C5—C6—C1	116.82 (12)	C11—C12—H12B	109.5
C5—C6—C11	117.25 (11)	H12A—C12—H12B	109.5
C1—C6—C11	125.93 (12)	C11—C12—H12C	109.5
O3—C7—C8	106.80 (11)	H12A—C12—H12C	109.5
O3—C7—H7A	110.4	H12B—C12—H12C	109.5
C8—C7—H7A	110.4	C8—O1—H1	109.5
O3—C7—H7B	110.4	C1—O3—C7	119.30 (10)
C8—C7—H7B	110.4	C3—O4—C9	117.02 (10)
H7A—C7—H7B	108.6	C10—O6—H6	109.5
O2—C8—O1	124.70 (13)

O3—C1—C2—C3	−179.66 (12)	O3—C7—C8—O1	163.06 (12)
C6—C1—C2—C3	−0.3 (2)	O4—C9—C10—O5	2.36 (19)
C1—C2—C3—O4	−179.26 (11)	O4—C9—C10—O6	−178.61 (11)
C1—C2—C3—C4	0.6 (2)	C5—C6—C11—O7	−9.3 (2)
O4—C3—C4—C5	179.78 (12)	C1—C6—C11—O7	171.32 (14)
C2—C3—C4—C5	−0.1 (2)	C5—C6—C11—C12	168.98 (14)
C3—C4—C5—C6	−0.8 (2)	C1—C6—C11—C12	−10.4 (2)
C4—C5—C6—C1	1.1 (2)	C2—C1—O3—C7	2.9 (2)
C4—C5—C6—C11	−178.34 (13)	C6—C1—O3—C7	−176.45 (12)
O3—C1—C6—C5	178.87 (12)	C8—C7—O3—C1	−176.25 (11)
C2—C1—C6—C5	−0.52 (19)	C2—C3—O4—C9	−176.96 (11)
O3—C1—C6—C11	−1.8 (2)	C4—C3—O4—C9	3.1 (2)
C2—C1—C6—C11	178.85 (12)	C10—C9—O4—C3	−175.88 (11)
O3—C7—C8—O2	−17.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.83	2.6530 (14)	180
O6—H6···O5ⁱⁱ	0.82	1.83	2.6352 (15)	167
C2—H2···O7ⁱⁱⁱ	0.93	2.44	3.3566 (17)	168
C4—H4···O6^iv	0.93	2.52	3.4392 (19)	169

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂O₇
M_r	268.22
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	5.1351 (6), 7.8346 (9), 15.6157 (18)
α, β, γ (°)	86.217 (2), 81.321 (1), 72.101 (2)
V (Å³)	590.86 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.12 × 0.10 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.985, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	3902, 2049, 1860
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.120, 1.05
No. of reflections	2049
No. of parameters	176
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.23

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.83	2.6530 (14)	180
O6—H6···O5ⁱⁱ	0.82	1.83	2.6352 (15)	167
C2—H2···O7ⁱⁱⁱ	0.93	2.44	3.3566 (17)	168
C4—H4···O6^iv	0.93	2.52	3.4392 (19)	169

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

Acknowledgements

This study was funded by Jiangxi Provincial Department of Education (GJJ08433) and the Doctoral Research Initiating Project of Jiujiang University.

References

Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, C., Li, H., Liu, D. & Liu, M. (2007). Acta Cryst. E63, o4210. Web of Science CSD CrossRef IUCr Journals Google Scholar