2,2′-[2,3,5,6-Tetra­methyl-p-phenyl­enebis­(methyl­eneoxy)]dibenzoic acid

Hu, T.

doi:10.1107/S1600536810011220

organic compounds

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Volume 66| Part 4| April 2010| Page o995

doi:10.1107/S1600536810011220

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2,2′-[2,3,5,6-Tetramethyl-p-phenylenebis(methyleneoxy)]dibenzoic acid

Tuoping Hu ^a ^*

^aDepartment of Chemistry, North University of China, Taiyuan, Shanxi 030051, People's Republic of China
^*Correspondence e-mail: hutuopingsx@yahoo.com.cn

(Received 29 January 2010; accepted 24 March 2010; online 31 March 2010)

The asymmetric unit of the title compound, C₂₆H₂₆O₆, contains only a half-molecule, the other half being generated by an inversion center. The two carboxyphenoxymethyl units occupy the 1,4-positions of the central aromatic ring. The central ring and the six linked C atoms are almost planar, with a maximum deviation of 0.0286 (17) Å, and the plane makes a dihedral angle of 75.50 (6)° with the benzene ring. In the crystal, strong O—H⋯O hydrogen bonds between the carboxyl groups of adjacent molecules and C—H⋯π interactions link the molecules into zigzag chains along (220) and ( $[\overline{1}]$ 10); the two types of chain are arranged alternately, forming a three-dimensional framework.

Related literature

For a structure with a similar central ring, see: Britton (2003 ). For structures with similar hydrogen-bonded carboxylate groups, see: Bailey & Brown (1967 ); Glidewell et al. (2004 ).

Experimental

Crystal data

C₂₆H₂₆O₆
M_r = 434.47
Monoclinic, P 2₁ /c
a = 9.2841 (16) Å
b = 8.6936 (15) Å
c = 14.075 (2) Å
β = 96.902 (3)°
V = 1127.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.16 × 0.12 × 0.06 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.985, T_max = 0.994
6437 measured reflections
2322 independent reflections
1269 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.157
S = 1.02
2322 reflections
159 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the central C9,C10,C12′,C9′C10′,C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2A—H2A⋯O1ⁱ	0.82	1.83	2.624 (9)	164
O2B—H2B⋯O1ⁱ	0.82	1.91	2.721 (16)	168
C5—H5⋯Cg1ⁱⁱ	0.93	2.80	3.356 (5)	120
Symmetry codes: (i) -x+1, -y, -z; (ii) $[-x-1, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; 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 global, I. DOI: 10.1107/S1600536810011220/bq2194sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810011220/bq2194Isup2.hkl

checkCIF report

Comment top

The title compound (I), was designed as a ligand for preparing MOF materials. This paper reports its single crystal structure in the solid state. The asymmetric unit contains only half of the molecule, with the other half generated by an inversion center at (0,1/2,0). (Fig 1.). The two branches of benzenic-carboxylate acid groups of the title compound occupy the 1, 4 positions of the central aromatic ring to form a line. The central ring with its linked six C atoms, similar to the one observed in Britton (2003), is almost planar, with a maxima deviation of -0.0286 (17)° for C13 and makes a dihedral angle of 75.50 (6)° with the benzene ring. Strong C–H···π bond was observed in the structure, with a perpendicular distance of 2.700 (3)° to the C9 C10-C12-C9_iC10_iC12_i ring plane (i:-x, -y, -z). Meanwhile, the structure of the two carboxylate groups linked by the strong H-bond (Table 1) is comparable to that described in Bailey & Brown (1967) and Glidewell et al. (2004). Strong hydrogen bondings between the carboxylate groups of the adjacent molecules link the molecules of title compound into zig-zag chains along (220) and (-110) directions, respectively (Fig. 2), and these two chains were arranged alternatively to form a 3D framework (Fig. 3).

Related literature top

For a structure with a similar central ring, see: Britton (2003). For structures with similar hydrogen-bonded carboxylate groups, see: Bailey & Brown (1967); Glidewell et al. (2004).

Experimental top

1,4-bis(bromomethyl)-2,3,5,6-tetramethylbenzene (3.2 g, 10.0 mmol), methyl salicylate (3.08 g, 22.0 mmol) and K₂CO₃ (3.04 g, 22 mmol) were put into 40 ml of acetone and the mixture was heated to reflux for 6 hours. The resulting mixture was filtrated while it was still hot. Lots of white precipitate was formed when the filtrate was cooled down to room temperature. The precipitate was filtrated and was put into 30 ml methanol. NaOH aqueous solution (20 ml, 2 mol/L) was added and the solution was stirred for 8 hours under refluxing. After cooling to room temperature, the pH value of the clear solution was adjusted to 2 by dilute hydrochloric acid. The clear solution was allowed to evaporate slowly under inert atmosphere. Prismatic crystals of the title compound were obtained after 2 days. The crystals were filtered, washed by cold EtOH and dried in air.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (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. Molecular structure showing 50% probability displacement ellipsoids. The atoms marked with A are derived from the reference atoms by means of the (- x, 1 - y, - z) symmetry transformation..
	Fig. 2. Zig-zag chain along (220) direction in the structure. Strong hydrogen bondings are shown as dash lines.
	Fig. 3. Packing diagram viewed down the c axis.

2,2'-[2,3,5,6-Tetramethyl-p-phenylenebis(methyleneoxy)]dibenzoic acid top

Crystal data top

C₂₆H₂₆O₆	F(000) = 460
M_r = 434.47	D_x = 1.279 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1055 reflections
a = 9.2841 (16) Å	θ = 2.8–27.5°
b = 8.6936 (15) Å	µ = 0.09 mm⁻¹
c = 14.075 (2) Å	T = 293 K
β = 96.902 (3)°	Prism, colorless
V = 1127.8 (3) Å³	0.16 × 0.12 × 0.06 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	2322 independent reflections
Radiation source: fine-focus sealed tube	1269 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
phi and ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→12
T_min = 0.985, T_max = 0.994	k = −11→11
6437 measured reflections	l = −16→18

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) = 0.157	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0659P)² + 0.1641P] where P = (F_o² + 2F_c²)/3
2322 reflections	(Δ/σ)_max < 0.001
159 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₂₆H₂₆O₆	V = 1127.8 (3) Å³
M_r = 434.47	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.2841 (16) Å	µ = 0.09 mm⁻¹
b = 8.6936 (15) Å	T = 293 K
c = 14.075 (2) Å	0.16 × 0.12 × 0.06 mm
β = 96.902 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2322 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1269 reflections with I > 2σ(I)
T_min = 0.985, T_max = 0.994	R_int = 0.033
6437 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.157	H-atom parameters constrained
S = 1.02	Δρ_max = 0.23 e Å⁻³
2322 reflections	Δρ_min = −0.15 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 > 2sigma(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	Occ. (<1)
C1	0.4303 (2)	0.0417 (3)	0.12146 (17)	0.0593 (6)
C2	0.3798 (2)	0.0589 (3)	0.21720 (15)	0.0552 (6)
C3	0.4391 (3)	−0.0387 (3)	0.29015 (17)	0.0711 (7)
H3	0.5065	−0.1123	0.2768	0.085*
C4	0.4006 (3)	−0.0291 (3)	0.38111 (18)	0.0820 (8)
H4	0.4405	−0.0963	0.4286	0.098*
C5	0.3027 (3)	0.0805 (3)	0.40112 (17)	0.0775 (8)
H5	0.2774	0.0885	0.4629	0.093*
C6	0.2413 (3)	0.1787 (3)	0.33116 (17)	0.0666 (7)
H6	0.1750	0.2526	0.3459	0.080*
C7	0.2781 (2)	0.1680 (3)	0.23858 (15)	0.0558 (6)
C8	0.1090 (3)	0.3686 (3)	0.18341 (18)	0.0764 (8)
H8A	0.1458	0.4480	0.2283	0.092*
H8B	0.0318	0.3139	0.2097	0.092*
C9	0.0536 (3)	0.4386 (3)	0.08832 (18)	0.0666 (7)
C10	−0.0399 (3)	0.3513 (3)	0.0242 (2)	0.0687 (7)
C11	−0.0835 (3)	0.1899 (3)	0.0519 (2)	0.1008 (10)
H11A	−0.1073	0.1293	−0.0048	0.151*
H11B	−0.1664	0.1959	0.0865	0.151*
H11C	−0.0043	0.1428	0.0916	0.151*
C12	0.0955 (2)	0.5869 (3)	0.06413 (19)	0.0687 (7)
C13	0.2028 (3)	0.6782 (4)	0.1319 (2)	0.1005 (10)
H13A	0.2806	0.7135	0.0983	0.151*
H13B	0.2412	0.6137	0.1843	0.151*
H13C	0.1545	0.7649	0.1560	0.151*
O1	0.3567 (2)	0.0876 (2)	0.04745 (12)	0.0919 (7)
O2A	0.5605 (9)	−0.0059 (16)	0.1171 (6)	0.076 (3)	0.59 (4)
H2A	0.5699	−0.0296	0.0618	0.114*	0.59 (4)
O2B	0.524 (3)	−0.059 (4)	0.1191 (11)	0.130 (6)	0.41 (4)
H2B	0.5576	−0.0543	0.0678	0.196*	0.41 (4)
O3	0.22344 (16)	0.26410 (18)	0.16631 (11)	0.0674 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0584 (15)	0.0585 (15)	0.0617 (15)	0.0095 (12)	0.0096 (12)	−0.0021 (11)
C2	0.0541 (13)	0.0586 (13)	0.0532 (13)	0.0005 (11)	0.0072 (10)	−0.0003 (10)
C3	0.0738 (16)	0.0709 (16)	0.0683 (16)	0.0109 (13)	0.0072 (13)	0.0078 (13)
C4	0.094 (2)	0.092 (2)	0.0604 (16)	0.0041 (17)	0.0079 (14)	0.0189 (14)
C5	0.0815 (18)	0.096 (2)	0.0577 (15)	−0.0132 (16)	0.0189 (14)	0.0057 (15)
C6	0.0649 (15)	0.0753 (17)	0.0631 (15)	−0.0003 (13)	0.0218 (12)	−0.0003 (13)
C7	0.0540 (13)	0.0596 (14)	0.0553 (13)	−0.0030 (11)	0.0122 (10)	0.0025 (11)
C8	0.0746 (16)	0.0790 (18)	0.0793 (17)	0.0215 (14)	0.0239 (14)	−0.0003 (14)
C9	0.0591 (14)	0.0666 (16)	0.0768 (16)	0.0177 (12)	0.0189 (13)	0.0001 (13)
C10	0.0618 (15)	0.0567 (15)	0.0899 (18)	0.0113 (12)	0.0192 (14)	0.0024 (14)
C11	0.100 (2)	0.072 (2)	0.130 (3)	−0.0029 (16)	0.0143 (19)	0.0104 (17)
C12	0.0569 (14)	0.0634 (16)	0.0872 (18)	0.0098 (12)	0.0143 (13)	−0.0102 (14)
C13	0.092 (2)	0.094 (2)	0.112 (2)	−0.0043 (18)	0.0007 (18)	−0.0085 (18)
O1	0.0932 (13)	0.1265 (17)	0.0561 (11)	0.0414 (12)	0.0097 (10)	0.0044 (10)
O2A	0.062 (4)	0.116 (6)	0.052 (3)	0.028 (3)	0.011 (3)	0.003 (3)
O2B	0.160 (11)	0.133 (12)	0.115 (8)	0.077 (9)	0.088 (7)	0.054 (6)
O3	0.0686 (10)	0.0736 (11)	0.0631 (10)	0.0220 (8)	0.0207 (8)	0.0080 (8)

Geometric parameters (Å, º) top

C1—O2B	1.237 (16)	C8—H8A	0.9700
C1—O1	1.241 (3)	C8—H8B	0.9700
C1—O2A	1.286 (9)	C9—C10	1.399 (3)
C1—C2	1.487 (3)	C9—C12	1.401 (3)
C2—C3	1.393 (3)	C10—C12ⁱ	1.395 (3)
C2—C7	1.397 (3)	C10—C11	1.524 (4)
C3—C4	1.372 (3)	C11—H11A	0.9600
C3—H3	0.9300	C11—H11B	0.9600
C4—C5	1.369 (4)	C11—H11C	0.9600
C4—H4	0.9300	C12—C10ⁱ	1.395 (3)
C5—C6	1.375 (3)	C12—C13	1.518 (4)
C5—H5	0.9300	C13—H13A	0.9600
C6—C7	1.389 (3)	C13—H13B	0.9600
C6—H6	0.9300	C13—H13C	0.9600
C7—O3	1.366 (3)	O2A—H2A	0.8200
C8—O3	1.440 (3)	O2B—H2B	0.8200
C8—C9	1.503 (3)

O2B—C1—O1	121.6 (9)	C9—C8—H8B	110.4
O1—C1—O2A	119.3 (5)	H8A—C8—H8B	108.6
O2B—C1—C2	113.3 (7)	C10—C9—C12	120.8 (2)
O1—C1—C2	121.8 (2)	C10—C9—C8	118.3 (2)
O2A—C1—C2	118.4 (4)	C12—C9—C8	120.9 (2)
C3—C2—C7	118.2 (2)	C12ⁱ—C10—C9	120.0 (2)
C3—C2—C1	117.9 (2)	C12ⁱ—C10—C11	120.1 (2)
C7—C2—C1	124.0 (2)	C9—C10—C11	119.8 (2)
C4—C3—C2	121.8 (2)	C10—C11—H11A	109.5
C4—C3—H3	119.1	C10—C11—H11B	109.5
C2—C3—H3	119.1	H11A—C11—H11B	109.5
C5—C4—C3	119.2 (2)	C10—C11—H11C	109.5
C5—C4—H4	120.4	H11A—C11—H11C	109.5
C3—C4—H4	120.4	H11B—C11—H11C	109.5
C4—C5—C6	120.9 (2)	C10ⁱ—C12—C9	119.2 (2)
C4—C5—H5	119.6	C10ⁱ—C12—C13	120.2 (3)
C6—C5—H5	119.6	C9—C12—C13	120.6 (3)
C5—C6—C7	120.2 (2)	C12—C13—H13A	109.5
C5—C6—H6	119.9	C12—C13—H13B	109.5
C7—C6—H6	119.9	H13A—C13—H13B	109.5
O3—C7—C6	123.1 (2)	C12—C13—H13C	109.5
O3—C7—C2	117.07 (19)	H13A—C13—H13C	109.5
C6—C7—C2	119.8 (2)	H13B—C13—H13C	109.5
O3—C8—C9	106.66 (18)	C1—O2A—H2A	109.5
O3—C8—H8A	110.4	C1—O2B—H2B	109.5
C9—C8—H8A	110.4	C7—O3—C8	118.47 (17)
O3—C8—H8B	110.4

O2B—C1—C2—C3	−2 (2)	C3—C2—C7—C6	1.4 (3)
O1—C1—C2—C3	158.1 (2)	C1—C2—C7—C6	−177.8 (2)
O2A—C1—C2—C3	−30.0 (8)	O3—C8—C9—C10	78.2 (3)
O2B—C1—C2—C7	178 (2)	O3—C8—C9—C12	−101.3 (2)
O1—C1—C2—C7	−22.7 (4)	C12—C9—C10—C12ⁱ	−1.6 (4)
O2A—C1—C2—C7	149.2 (8)	C8—C9—C10—C12ⁱ	179.0 (2)
C7—C2—C3—C4	−0.4 (4)	C12—C9—C10—C11	179.7 (2)
C1—C2—C3—C4	178.9 (2)	C8—C9—C10—C11	0.3 (3)
C2—C3—C4—C5	−0.8 (4)	C10—C9—C12—C10ⁱ	1.5 (4)
C3—C4—C5—C6	1.0 (4)	C8—C9—C12—C10ⁱ	−179.0 (2)
C4—C5—C6—C7	0.0 (4)	C10—C9—C12—C13	−177.0 (2)
C5—C6—C7—O3	−178.6 (2)	C8—C9—C12—C13	2.5 (3)
C5—C6—C7—C2	−1.3 (3)	C6—C7—O3—C8	−8.1 (3)
C3—C2—C7—O3	178.9 (2)	C2—C7—O3—C8	174.5 (2)
C1—C2—C7—O3	−0.3 (3)	C9—C8—O3—C7	−170.4 (2)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the central C9,C10,C12',C9'C10',C12 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O2A—H2A···O1ⁱⁱ	0.82	1.83	2.624 (9)	164
O2B—H2B···O1ⁱⁱ	0.82	1.91	2.721 (16)	168
C5—H5···Cg1ⁱⁱⁱ	0.93	2.80	3.356 (5)	120

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

Experimental details

Crystal data
Chemical formula	C₂₆H₂₆O₆
M_r	434.47
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.2841 (16), 8.6936 (15), 14.075 (2)
β (°)	96.902 (3)
V (Å³)	1127.8 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.16 × 0.12 × 0.06

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.985, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	6437, 2322, 1269
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.157, 1.02
No. of reflections	2322
No. of parameters	159
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.15

Computer programs: SMART (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the central C9,C10,C12',C9'C10',C12 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O2A—H2A···O1ⁱ	0.82	1.83	2.624 (9)	164.1
O2B—H2B···O1ⁱ	0.82	1.91	2.721 (16)	168.4
C5—H5···Cg1ⁱⁱ	0.93	2.80	3.356 (5)	119.5

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

Acknowledgements

The author is grateful for funding support from the Natural Science Foundation of Shanxi Province (2007011033), the program of Technological Industrialization at the University of Shanxi Province (20070308) and the start-up fund of the North University of China.

References

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