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Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): o995.
Published online 2010 March 31. doi:  10.1107/S1600536810011220
PMCID: PMC2983800

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

Abstract

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 (An external file that holds a picture, illustration, etc.
Object name is e-66-0o995-efi1.jpg10); 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 [triangle]). For structures with similar hydrogen-bonded carboxyl­ate groups, see: Bailey & Brown (1967 [triangle]); Glidewell et al. (2004 [triangle]).

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Object name is e-66-0o995-scheme1.jpg

Experimental

Crystal data

  • C26H26O6
  • M r = 434.47
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o995-efi2.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.050
  • wR(F 2) = 0.157
  • S = 1.02
  • 2322 reflections
  • 159 parameters
  • H-atom parameters constrained
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.15 e Å−3

Data collection: SMART (Bruker, 2007 [triangle]); cell refinement: SAINT-Plus (Bruker, 2007 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810011220/bq2194sup1.cif

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

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

Acknowledgments

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.

supplementary crystallographic information

Comment

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-C9iC10iC12i 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).

Experimental

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.

Refinement

All H atoms were positioned geometrically and refined using a riding model with C—H = 0.930 Å and Uiso(H) = 1.2 Ueq(C) for aromatic hydrogens, and with C—H = 0.960 Å and Uiso(H) = 1.5 Ueq(C) for H atoms of the methyl groups, and with C—H = 0.970 Å and Uiso(H) = 1.2 Ueq(C) for H atoms of the methylene group, and with O—H = 0.820 Å and Uiso(H) = 1.2 Ueq(O) for the hydroxide H atom, respectively. O2 atom was treated as disordered in two positions of O2a and O2b with the occupation factors of 0.58, and 0.42, respectively.

Figures

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.

Crystal data

C26H26O6F(000) = 460
Mr = 434.47Dx = 1.279 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1055 reflections
a = 9.2841 (16) Åθ = 2.8–27.5°
b = 8.6936 (15) ŵ = 0.09 mm1
c = 14.075 (2) ÅT = 293 K
β = 96.902 (3)°Prism, colorless
V = 1127.8 (3) Å30.16 × 0.12 × 0.06 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer2322 independent reflections
Radiation source: fine-focus sealed tube1269 reflections with I > 2σ(I)
graphiteRint = 0.033
phi and ω scansθmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −10→12
Tmin = 0.985, Tmax = 0.994k = −11→11
6437 measured reflectionsl = −16→18

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.157H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.0659P)2 + 0.1641P] where P = (Fo2 + 2Fc2)/3
2322 reflections(Δ/σ)max < 0.001
159 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = −0.15 e Å3

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 > 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)

xyzUiso*/UeqOcc. (<1)
C10.4303 (2)0.0417 (3)0.12146 (17)0.0593 (6)
C20.3798 (2)0.0589 (3)0.21720 (15)0.0552 (6)
C30.4391 (3)−0.0387 (3)0.29015 (17)0.0711 (7)
H30.5065−0.11230.27680.085*
C40.4006 (3)−0.0291 (3)0.38111 (18)0.0820 (8)
H40.4405−0.09630.42860.098*
C50.3027 (3)0.0805 (3)0.40112 (17)0.0775 (8)
H50.27740.08850.46290.093*
C60.2413 (3)0.1787 (3)0.33116 (17)0.0666 (7)
H60.17500.25260.34590.080*
C70.2781 (2)0.1680 (3)0.23858 (15)0.0558 (6)
C80.1090 (3)0.3686 (3)0.18341 (18)0.0764 (8)
H8A0.14580.44800.22830.092*
H8B0.03180.31390.20970.092*
C90.0536 (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−0.10730.1293−0.00480.151*
H11B−0.16640.19590.08650.151*
H11C−0.00430.14280.09160.151*
C120.0955 (2)0.5869 (3)0.06413 (19)0.0687 (7)
C130.2028 (3)0.6782 (4)0.1319 (2)0.1005 (10)
H13A0.28060.71350.09830.151*
H13B0.24120.61370.18430.151*
H13C0.15450.76490.15600.151*
O10.3567 (2)0.0876 (2)0.04745 (12)0.0919 (7)
O2A0.5605 (9)−0.0059 (16)0.1171 (6)0.076 (3)0.59 (4)
H2A0.5699−0.02960.06180.114*0.59 (4)
O2B0.524 (3)−0.059 (4)0.1191 (11)0.130 (6)0.41 (4)
H2B0.5576−0.05430.06780.196*0.41 (4)
O30.22344 (16)0.26410 (18)0.16631 (11)0.0674 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0584 (15)0.0585 (15)0.0617 (15)0.0095 (12)0.0096 (12)−0.0021 (11)
C20.0541 (13)0.0586 (13)0.0532 (13)0.0005 (11)0.0072 (10)−0.0003 (10)
C30.0738 (16)0.0709 (16)0.0683 (16)0.0109 (13)0.0072 (13)0.0078 (13)
C40.094 (2)0.092 (2)0.0604 (16)0.0041 (17)0.0079 (14)0.0189 (14)
C50.0815 (18)0.096 (2)0.0577 (15)−0.0132 (16)0.0189 (14)0.0057 (15)
C60.0649 (15)0.0753 (17)0.0631 (15)−0.0003 (13)0.0218 (12)−0.0003 (13)
C70.0540 (13)0.0596 (14)0.0553 (13)−0.0030 (11)0.0122 (10)0.0025 (11)
C80.0746 (16)0.0790 (18)0.0793 (17)0.0215 (14)0.0239 (14)−0.0003 (14)
C90.0591 (14)0.0666 (16)0.0768 (16)0.0177 (12)0.0189 (13)0.0001 (13)
C100.0618 (15)0.0567 (15)0.0899 (18)0.0113 (12)0.0192 (14)0.0024 (14)
C110.100 (2)0.072 (2)0.130 (3)−0.0029 (16)0.0143 (19)0.0104 (17)
C120.0569 (14)0.0634 (16)0.0872 (18)0.0098 (12)0.0143 (13)−0.0102 (14)
C130.092 (2)0.094 (2)0.112 (2)−0.0043 (18)0.0007 (18)−0.0085 (18)
O10.0932 (13)0.1265 (17)0.0561 (11)0.0414 (12)0.0097 (10)0.0044 (10)
O2A0.062 (4)0.116 (6)0.052 (3)0.028 (3)0.011 (3)0.003 (3)
O2B0.160 (11)0.133 (12)0.115 (8)0.077 (9)0.088 (7)0.054 (6)
O30.0686 (10)0.0736 (11)0.0631 (10)0.0220 (8)0.0207 (8)0.0080 (8)

Geometric parameters (Å, °)

C1—O2B1.237 (16)C8—H8A0.9700
C1—O11.241 (3)C8—H8B0.9700
C1—O2A1.286 (9)C9—C101.399 (3)
C1—C21.487 (3)C9—C121.401 (3)
C2—C31.393 (3)C10—C12i1.395 (3)
C2—C71.397 (3)C10—C111.524 (4)
C3—C41.372 (3)C11—H11A0.9600
C3—H30.9300C11—H11B0.9600
C4—C51.369 (4)C11—H11C0.9600
C4—H40.9300C12—C10i1.395 (3)
C5—C61.375 (3)C12—C131.518 (4)
C5—H50.9300C13—H13A0.9600
C6—C71.389 (3)C13—H13B0.9600
C6—H60.9300C13—H13C0.9600
C7—O31.366 (3)O2A—H2A0.8200
C8—O31.440 (3)O2B—H2B0.8200
C8—C91.503 (3)
O2B—C1—O1121.6 (9)C9—C8—H8B110.4
O1—C1—O2A119.3 (5)H8A—C8—H8B108.6
O2B—C1—C2113.3 (7)C10—C9—C12120.8 (2)
O1—C1—C2121.8 (2)C10—C9—C8118.3 (2)
O2A—C1—C2118.4 (4)C12—C9—C8120.9 (2)
C3—C2—C7118.2 (2)C12i—C10—C9120.0 (2)
C3—C2—C1117.9 (2)C12i—C10—C11120.1 (2)
C7—C2—C1124.0 (2)C9—C10—C11119.8 (2)
C4—C3—C2121.8 (2)C10—C11—H11A109.5
C4—C3—H3119.1C10—C11—H11B109.5
C2—C3—H3119.1H11A—C11—H11B109.5
C5—C4—C3119.2 (2)C10—C11—H11C109.5
C5—C4—H4120.4H11A—C11—H11C109.5
C3—C4—H4120.4H11B—C11—H11C109.5
C4—C5—C6120.9 (2)C10i—C12—C9119.2 (2)
C4—C5—H5119.6C10i—C12—C13120.2 (3)
C6—C5—H5119.6C9—C12—C13120.6 (3)
C5—C6—C7120.2 (2)C12—C13—H13A109.5
C5—C6—H6119.9C12—C13—H13B109.5
C7—C6—H6119.9H13A—C13—H13B109.5
O3—C7—C6123.1 (2)C12—C13—H13C109.5
O3—C7—C2117.07 (19)H13A—C13—H13C109.5
C6—C7—C2119.8 (2)H13B—C13—H13C109.5
O3—C8—C9106.66 (18)C1—O2A—H2A109.5
O3—C8—H8A110.4C1—O2B—H2B109.5
C9—C8—H8A110.4C7—O3—C8118.47 (17)
O3—C8—H8B110.4
O2B—C1—C2—C3−2(2)C3—C2—C7—C61.4 (3)
O1—C1—C2—C3158.1 (2)C1—C2—C7—C6−177.8 (2)
O2A—C1—C2—C3−30.0 (8)O3—C8—C9—C1078.2 (3)
O2B—C1—C2—C7178 (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—C7149.2 (8)C8—C9—C10—C12i179.0 (2)
C7—C2—C3—C4−0.4 (4)C12—C9—C10—C11179.7 (2)
C1—C2—C3—C4178.9 (2)C8—C9—C10—C110.3 (3)
C2—C3—C4—C5−0.8 (4)C10—C9—C12—C10i1.5 (4)
C3—C4—C5—C61.0 (4)C8—C9—C12—C10i−179.0 (2)
C4—C5—C6—C70.0 (4)C10—C9—C12—C13−177.0 (2)
C5—C6—C7—O3−178.6 (2)C8—C9—C12—C132.5 (3)
C5—C6—C7—C2−1.3 (3)C6—C7—O3—C8−8.1 (3)
C3—C2—C7—O3178.9 (2)C2—C7—O3—C8174.5 (2)
C1—C2—C7—O3−0.3 (3)C9—C8—O3—C7−170.4 (2)

Symmetry codes: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the central C9,C10,C12',C9'C10',C12 ring.
D—H···AD—HH···AD···AD—H···A
O2A—H2A···O1ii0.821.832.624 (9)164
O2B—H2B···O1ii0.821.912.721 (16)168
C5—H5···Cg1iii0.932.803.356 (5)120

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BQ2194).

References

  • Bailey, M. & Brown, C. J. (1967). Acta Cryst.22, 387–391.
  • Britton, D. (2003). Acta Cryst. E59, o1089–o1091.
  • Bruker (2007). SMART, and SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2004). Acta Cryst. C60, o361–o363. [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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