3,3′-Dimeth­oxy-4,4′-(propane-1,3-diyl­dioxy)dibenzoic acid

Deng, R.-X.; Liu, P.; Zhou, W.-Y.

doi:10.1107/S1600536807047216

3,3′-Dimethoxy-4,4′-(propane-1,3-diyldioxy)dibenzoic acid

In the title compound, C₁₉H₂₀O₈, the two benzene rings are approximately perpendicular to each other [dihedral angle = 83.7 (3)°]. The methoxy and carboxyl groups do not deviate from the planes of the respective benzene rings. Intermolecular O—H

O hydrogen bonds stabilize the crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047216/at2410sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047216/at2410Isup2.hkl Contains datablock I

CCDC reference: 667259

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Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.004 Å
R factor = 0.050
wR factor = 0.135
Data-to-parameter ratio = 14.3

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PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        400 Deg.

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Comment top

The oxygen atoms of carboxyl group can coordinate to metal ions forming various complexes with novel structures. In this paper we synthesize a special flexible ligand containing double aromatic acid connected by propyl spacer. Under nitrogen atmosphere we first made the title compound (I). The single crystals of (I) were obtained and its molecular and crystal structures were characterized by single-crystal X-ray diffraction.

The molecular structure of (I) and the atom-numbering scheme are shown in Fig. 1. The dihedral angle between the two benzene ring is 96.3 (3)°, indicating that the two benzene rings are approximately perpendicular to each other. The two methoxy groups are nearly planar with their benzene rings (C2–C7) and (C12–C17) with the r.m.s deviations of 0.0397 (3) and 0.255 (3) Å, respectively. Similarly, two r.m.s deviations of the two carbonyl groups from these two benzene rings are 0.0111 and 0.07233) Å, respectively. The intermolecular O—H···O hydrogen-bonded between the hydroxyl and carbonyl groups form a centrosymmetric dimer (Table 2) and stabilize the crystal structure.

Related literature top

For related literature, see: Thurston et al. (1996).

Experimental top

The title compound (I) was synthesized according to the literature procedure (Thurston et al., 1996). A mixture of 200 mg of the title compound and 10 ml water was stirred for 1 h and then heated to 413 K for 2 d. Single crystals of (I) suitable for X-ray analysis were obtained after they are cooled to room temperature at 10 ^oC/h.

Single crystals of (I) suitable for X-ray analysis were obtained by recrystallized under autogenous pressure.

Structure description top

For related literature, see: Thurston et al. (1996).

Computing details top

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

Figures top

Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level.

3,3'-Dimethoxy-4,4'-(propane-1,3-diyldioxy)dibenzoic acid top

Crystal data top

C₁₉H₂₀O₈	Z = 2
M_r = 376.35	F(000) = 396
Triclinic, P1	D_x = 1.415 Mg m⁻³
Hall symbol: -P 1	Melting point: 512 K
a = 4.8729 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.9736 (18) Å	Cell parameters from 1045 reflections
c = 23.604 (6) Å	θ = 2.6–26.0°
α = 93.744 (4)°	µ = 0.11 mm⁻¹
β = 94.260 (4)°	T = 294 K
γ = 104.173 (4)°	Plate, colourless
V = 883.4 (3) Å³	0.16 × 0.12 × 0.08 mm

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	3537 independent reflections
Radiation source: fine-focus sealed tube	1907 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
φ and ω scans	θ_max = 26.4°, θ_min = 0.9°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −6→4
T_min = 0.982, T_max = 0.991	k = −9→9
5097 measured reflections	l = −29→28

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) = 0.135	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0482P)² + 0.2554P] where P = (F_o² + 2F_c²)/3
3537 reflections	(Δ/σ)_max < 0.001
248 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₉H₂₀O₈	γ = 104.173 (4)°
M_r = 376.35	V = 883.4 (3) Å³
Triclinic, P1	Z = 2
a = 4.8729 (11) Å	Mo Kα radiation
b = 7.9736 (18) Å	µ = 0.11 mm⁻¹
c = 23.604 (6) Å	T = 294 K
α = 93.744 (4)°	0.16 × 0.12 × 0.08 mm
β = 94.260 (4)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	3537 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1907 reflections with I > 2σ(I)
T_min = 0.982, T_max = 0.991	R_int = 0.025
5097 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.135	H-atom parameters constrained
S = 0.99	Δρ_max = 0.21 e Å⁻³
3537 reflections	Δρ_min = −0.20 e Å⁻³
248 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
O1	1.3675 (5)	1.0676 (3)	0.43874 (9)	0.0579 (6)
H1	1.4940	1.0828	0.4649	0.087*
O2	1.1815 (4)	0.8428 (3)	0.48774 (8)	0.0556 (6)
O3	0.2594 (5)	0.5435 (3)	0.36351 (8)	0.0546 (6)
O4	0.2585 (4)	0.7219 (2)	0.27527 (8)	0.0449 (5)
O5	−0.1359 (4)	1.0118 (2)	0.17115 (7)	0.0389 (5)
O6	−0.3414 (5)	1.2372 (2)	0.22523 (7)	0.0497 (6)
O7	−0.8275 (4)	1.5175 (3)	0.07122 (8)	0.0505 (6)
H7	−0.9377	1.5530	0.0500	0.076*
O8	−0.8096 (4)	1.3542 (3)	−0.00843 (8)	0.0476 (5)
C1	1.1723 (7)	0.9327 (4)	0.44555 (12)	0.0441 (7)
C2	0.9296 (6)	0.8816 (4)	0.40125 (11)	0.0419 (7)
C3	0.9210 (6)	0.9787 (4)	0.35512 (11)	0.0432 (7)
H3	1.0660	1.0776	0.3525	0.052*
C4	0.6972 (6)	0.9293 (4)	0.31276 (11)	0.0426 (7)
H4	0.6922	0.9957	0.2819	0.051*
C5	0.4823 (6)	0.7825 (4)	0.31606 (11)	0.0379 (7)
C6	0.4849 (6)	0.6843 (4)	0.36349 (11)	0.0410 (7)
C7	0.7098 (7)	0.7356 (4)	0.40541 (11)	0.0438 (7)
H7A	0.7141	0.6713	0.4368	0.053*
C8	0.2343 (9)	0.4518 (4)	0.41381 (14)	0.0752 (11)
H8A	0.3895	0.3982	0.4189	0.113*
H8B	0.0578	0.3642	0.4100	0.113*
H8C	0.2386	0.5317	0.4463	0.113*
C9	0.2334 (6)	0.8329 (4)	0.23078 (11)	0.0405 (7)
H9A	0.4022	0.8533	0.2103	0.049*
H9B	0.2139	0.9440	0.2469	0.049*
C10	−0.0230 (6)	0.7462 (3)	0.19106 (11)	0.0401 (7)
H10A	−0.1880	0.7192	0.2126	0.048*
H10B	0.0028	0.6378	0.1740	0.048*
C11	−0.0767 (6)	0.8586 (3)	0.14434 (11)	0.0408 (7)
H11A	0.0891	0.8903	0.1232	0.049*
H11B	−0.2370	0.7962	0.1180	0.049*
C12	−0.2660 (5)	1.1086 (3)	0.13794 (11)	0.0332 (6)
C13	−0.2889 (6)	1.0933 (3)	0.07897 (11)	0.0378 (7)
H13	−0.2030	1.0179	0.0595	0.045*
C14	−0.4406 (6)	1.1908 (3)	0.04883 (11)	0.0386 (7)
H14	−0.4568	1.1795	0.0092	0.046*
C15	−0.5676 (5)	1.3045 (3)	0.07725 (11)	0.0350 (6)
C16	−0.5356 (6)	1.3250 (3)	0.13690 (11)	0.0363 (7)
H16	−0.6171	1.4033	0.1562	0.044*
C17	−0.3841 (6)	1.2299 (3)	0.16731 (10)	0.0347 (6)
C18	−0.7436 (6)	1.3963 (3)	0.04375 (12)	0.0374 (7)
C19	−0.4814 (8)	1.3418 (4)	0.25887 (12)	0.0677 (11)
H19A	−0.4077	1.4619	0.2530	0.102*
H19B	−0.4482	1.3251	0.2985	0.102*
H19C	−0.6820	1.3082	0.2476	0.102*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0599 (15)	0.0580 (14)	0.0537 (14)	0.0173 (12)	−0.0168 (11)	0.0046 (11)
O2	0.0698 (15)	0.0620 (14)	0.0390 (12)	0.0269 (12)	−0.0092 (11)	0.0106 (11)
O3	0.0666 (15)	0.0452 (12)	0.0504 (13)	0.0107 (11)	−0.0021 (11)	0.0133 (10)
O4	0.0524 (13)	0.0423 (11)	0.0416 (12)	0.0164 (10)	−0.0068 (10)	0.0100 (9)
O5	0.0462 (12)	0.0398 (11)	0.0343 (10)	0.0204 (9)	−0.0055 (9)	0.0026 (8)
O6	0.0782 (15)	0.0501 (12)	0.0278 (10)	0.0310 (11)	−0.0003 (10)	0.0019 (9)
O7	0.0586 (15)	0.0558 (13)	0.0449 (12)	0.0321 (11)	−0.0064 (10)	0.0055 (10)
O8	0.0520 (13)	0.0617 (13)	0.0338 (11)	0.0253 (11)	−0.0035 (10)	0.0056 (10)
C1	0.053 (2)	0.0454 (19)	0.0386 (17)	0.0252 (17)	−0.0026 (15)	−0.0010 (14)
C2	0.0489 (19)	0.0464 (18)	0.0355 (16)	0.0242 (15)	−0.0009 (14)	0.0001 (13)
C3	0.0466 (19)	0.0475 (18)	0.0380 (17)	0.0170 (15)	0.0011 (14)	0.0053 (14)
C4	0.052 (2)	0.0465 (18)	0.0333 (16)	0.0204 (16)	0.0000 (14)	0.0073 (13)
C5	0.0439 (18)	0.0413 (16)	0.0327 (15)	0.0211 (14)	−0.0020 (13)	0.0010 (13)
C6	0.051 (2)	0.0372 (16)	0.0376 (17)	0.0177 (15)	0.0023 (14)	0.0026 (13)
C7	0.061 (2)	0.0452 (18)	0.0338 (16)	0.0292 (17)	0.0024 (15)	0.0082 (13)
C8	0.111 (3)	0.053 (2)	0.060 (2)	0.014 (2)	0.004 (2)	0.0254 (18)
C9	0.0412 (18)	0.0460 (17)	0.0377 (16)	0.0174 (14)	−0.0025 (13)	0.0093 (13)
C10	0.0467 (18)	0.0359 (16)	0.0402 (16)	0.0178 (14)	−0.0028 (14)	0.0011 (13)
C11	0.0451 (18)	0.0413 (16)	0.0376 (16)	0.0180 (14)	−0.0047 (13)	−0.0027 (13)
C12	0.0297 (15)	0.0353 (15)	0.0342 (15)	0.0081 (12)	−0.0026 (12)	0.0070 (12)
C13	0.0388 (17)	0.0441 (16)	0.0334 (16)	0.0161 (14)	0.0028 (13)	0.0033 (13)
C14	0.0377 (17)	0.0506 (17)	0.0271 (14)	0.0119 (14)	−0.0029 (13)	0.0044 (13)
C15	0.0316 (16)	0.0383 (15)	0.0358 (16)	0.0103 (13)	0.0001 (12)	0.0054 (12)
C16	0.0411 (17)	0.0331 (15)	0.0353 (16)	0.0112 (13)	0.0009 (13)	0.0031 (12)
C17	0.0408 (17)	0.0341 (15)	0.0293 (15)	0.0094 (13)	0.0016 (13)	0.0046 (12)
C18	0.0364 (17)	0.0370 (16)	0.0402 (17)	0.0120 (13)	−0.0002 (14)	0.0066 (13)
C19	0.120 (3)	0.056 (2)	0.0395 (18)	0.042 (2)	0.020 (2)	0.0039 (16)

Geometric parameters (Å, º) top

O1—C1	1.277 (3)	C8—H8A	0.9600
O1—H1	0.8200	C8—H8B	0.9600
O2—C1	1.269 (3)	C8—H8C	0.9600
O3—C6	1.365 (3)	C9—C10	1.495 (4)
O3—C8	1.432 (3)	C9—H9A	0.9700
O4—C5	1.369 (3)	C9—H9B	0.9700
O4—C9	1.434 (3)	C10—C11	1.513 (3)
O5—C12	1.363 (3)	C10—H10A	0.9700
O5—C11	1.441 (3)	C10—H10B	0.9700
O6—C17	1.363 (3)	C11—H11A	0.9700
O6—C19	1.437 (3)	C11—H11B	0.9700
O7—C18	1.294 (3)	C12—C13	1.383 (3)
O7—H7	0.8200	C12—C17	1.411 (3)
O8—C18	1.252 (3)	C13—C14	1.390 (3)
C1—C2	1.477 (4)	C13—H13	0.9300
C2—C3	1.380 (4)	C14—C15	1.383 (4)
C2—C7	1.390 (4)	C14—H14	0.9300
C3—C4	1.386 (4)	C15—C16	1.399 (3)
C3—H3	0.9300	C15—C18	1.476 (3)
C4—C5	1.377 (4)	C16—C17	1.379 (3)
C4—H4	0.9300	C16—H16	0.9300
C5—C6	1.408 (4)	C19—H19A	0.9600
C6—C7	1.384 (4)	C19—H19B	0.9600
C7—H7A	0.9300	C19—H19C	0.9600

C1—O1—H1	109.5	C9—C10—C11	112.2 (2)
C6—O3—C8	117.7 (2)	C9—C10—H10A	109.2
C5—O4—C9	116.2 (2)	C11—C10—H10A	109.2
C12—O5—C11	117.88 (19)	C9—C10—H10B	109.2
C17—O6—C19	118.7 (2)	C11—C10—H10B	109.2
C18—O7—H7	109.5	H10A—C10—H10B	107.9
O2—C1—O1	122.9 (3)	O5—C11—C10	107.4 (2)
O2—C1—C2	120.0 (3)	O5—C11—H11A	110.2
O1—C1—C2	117.1 (3)	C10—C11—H11A	110.2
C3—C2—C7	119.6 (3)	O5—C11—H11B	110.2
C3—C2—C1	119.9 (3)	C10—C11—H11B	110.2
C7—C2—C1	120.5 (3)	H11A—C11—H11B	108.5
C2—C3—C4	120.2 (3)	O5—C12—C13	124.3 (2)
C2—C3—H3	119.9	O5—C12—C17	115.9 (2)
C4—C3—H3	119.9	C13—C12—C17	119.8 (2)
C5—C4—C3	120.4 (3)	C12—C13—C14	120.0 (3)
C5—C4—H4	119.8	C12—C13—H13	120.0
C3—C4—H4	119.8	C14—C13—H13	120.0
O4—C5—C4	124.1 (2)	C15—C14—C13	120.6 (2)
O4—C5—C6	115.9 (3)	C15—C14—H14	119.7
C4—C5—C6	120.0 (3)	C13—C14—H14	119.7
O3—C6—C7	125.5 (3)	C14—C15—C16	119.5 (2)
O3—C6—C5	115.6 (3)	C14—C15—C18	118.9 (2)
C7—C6—C5	118.8 (3)	C16—C15—C18	121.6 (2)
C6—C7—C2	120.9 (3)	C17—C16—C15	120.4 (2)
C6—C7—H7A	119.5	C17—C16—H16	119.8
C2—C7—H7A	119.5	C15—C16—H16	119.8
O3—C8—H8A	109.5	O6—C17—C16	125.7 (2)
O3—C8—H8B	109.5	O6—C17—C12	114.7 (2)
H8A—C8—H8B	109.5	C16—C17—C12	119.6 (2)
O3—C8—H8C	109.5	O8—C18—O7	122.9 (2)
H8A—C8—H8C	109.5	O8—C18—C15	120.4 (2)
H8B—C8—H8C	109.5	O7—C18—C15	116.7 (2)
O4—C9—C10	108.4 (2)	O6—C19—H19A	109.5
O4—C9—H9A	110.0	O6—C19—H19B	109.5
C10—C9—H9A	110.0	H19A—C19—H19B	109.5
O4—C9—H9B	110.0	O6—C19—H19C	109.5
C10—C9—H9B	110.0	H19A—C19—H19C	109.5
H9A—C9—H9B	108.4	H19B—C19—H19C	109.5

O2—C1—C2—C3	−179.4 (2)	C12—O5—C11—C10	−162.3 (2)
O1—C1—C2—C3	−0.1 (4)	C9—C10—C11—O5	−63.3 (3)
O2—C1—C2—C7	0.1 (4)	C11—O5—C12—C13	−14.9 (4)
O1—C1—C2—C7	179.5 (3)	C11—O5—C12—C17	164.6 (2)
C7—C2—C3—C4	−1.0 (4)	O5—C12—C13—C14	176.1 (2)
C1—C2—C3—C4	178.5 (2)	C17—C12—C13—C14	−3.3 (4)
C2—C3—C4—C5	−0.4 (4)	C12—C13—C14—C15	0.5 (4)
C9—O4—C5—C4	−8.3 (4)	C13—C14—C15—C16	1.9 (4)
C9—O4—C5—C6	171.9 (2)	C13—C14—C15—C18	−175.7 (2)
C3—C4—C5—O4	−177.9 (2)	C14—C15—C16—C17	−1.5 (4)
C3—C4—C5—C6	1.8 (4)	C18—C15—C16—C17	176.1 (2)
C8—O3—C6—C7	7.6 (4)	C19—O6—C17—C16	5.1 (4)
C8—O3—C6—C5	−172.6 (2)	C19—O6—C17—C12	−172.9 (3)
O4—C5—C6—O3	−1.7 (3)	C15—C16—C17—O6	−179.2 (2)
C4—C5—C6—O3	178.5 (2)	C15—C16—C17—C12	−1.3 (4)
O4—C5—C6—C7	178.0 (2)	O5—C12—C17—O6	2.4 (3)
C4—C5—C6—C7	−1.7 (4)	C13—C12—C17—O6	−178.2 (2)
O3—C6—C7—C2	−180.0 (3)	O5—C12—C17—C16	−175.8 (2)
C5—C6—C7—C2	0.3 (4)	C13—C12—C17—C16	3.7 (4)
C3—C2—C7—C6	1.1 (4)	C14—C15—C18—O8	9.9 (4)
C1—C2—C7—C6	−178.5 (2)	C16—C15—C18—O8	−167.6 (2)
C5—O4—C9—C10	−179.4 (2)	C14—C15—C18—O7	−171.3 (2)
O4—C9—C10—C11	176.8 (2)	C16—C15—C18—O7	11.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.81	2.618 (3)	166
O7—H7···O8ⁱⁱ	0.82	1.84	2.658 (3)	174

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

Experimental details

Crystal data
Chemical formula	C₁₉H₂₀O₈
M_r	376.35
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	4.8729 (11), 7.9736 (18), 23.604 (6)
α, β, γ (°)	93.744 (4), 94.260 (4), 104.173 (4)
V (Å³)	883.4 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.16 × 0.12 × 0.08

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.982, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	5097, 3537, 1907
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.135, 0.99
No. of reflections	3537
No. of parameters	248
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.20

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