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Acta Crystallogr Sect E Struct Rep Online. 2009 January 1; 65(Pt 1): o170.
Published online 2008 December 20. doi:  10.1107/S1600536808041688
PMCID: PMC2968081

2,2′-(p-Phenyl­enedimethyl­ene)bis­(propane-1,3-diol)

Abstract

The mol­ecule of the title compound, C14H22O4, is centrosymmetric. In the crystal, the mol­ecules are linked through O—H(...)O hydrogen bonds into a three-dimensional network.

Related literature

For a related structure, see: Xi et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o170-scheme1.jpg

Experimental

Crystal data

  • C14H22O4
  • M r = 254.32
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o170-efi1.jpg
  • a = 9.939 (6) Å
  • b = 8.803 (5) Å
  • c = 15.366 (9) Å
  • V = 1344.5 (14) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 291 (2) K
  • 0.30 × 0.24 × 0.22 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.97, T max = 0.98
  • 7571 measured reflections
  • 1636 independent reflections
  • 1215 reflections with I > 2σ(I)
  • R int = 0.057

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.115
  • S = 1.08
  • 1636 reflections
  • 88 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.17 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808041688/gk2172sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808041688/gk2172Isup2.hkl

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

Acknowledgments

The authors are grateful to Jiangsu Polytechnic University, the Natural Science Foundation of China (No. 20872051) and the Key Laboratory of Fine Petrochemical Engineering of Jiangsu Province (KF0503) for finanical support.

supplementary crystallographic information

Comment

Reduction is a fundamental transformation in organic synthesis. Lithium aluminium hydride is used in organic synthesis as a powerful reducing agent.

The title molecule has a crystallographic inversion center located at the middle of the benzene ring. The trans-arrangement of two 1,3-dihydroxyisopropyl groups in the title compound was verified by X-ray crystallographic studies (Fig.1). The torsion angle C3—C4—C5—C6 is 165.14 (10) ° and the torsion angle of C3-C4-C5- C7 is -70.96 (13).

Experimental

Tetraethyl 2,2'-(p-phenylenedimethylene)dimalonate was prepared according to the literature procedure (Xi et al., 2008). In a flame-dryed, round-bottom flask was placed freshly distilled THF (80 ml) under dry nitrogen gas and the flask was placed in an ice-bath. Subsequently LiAlH4 (2.128 g, 56 mmol) was slowly added with stirring, followed by a dropwise addition of the solution of tetraethyl 2,2'-(p-phenylenedimethylene)dimalonate (2.95 g,7 mmol) in THF (20 ml) . After stirring for 3 h at room temperature, a saturated solution of Na2SO4(3 ml) was added. Stirring was continued for next 10 min. Then ethanol (8 mL) was added, the mixture was heated to 333 K. Lithium and aluminium salts were separated by filtration on celite. Filtrate was evaporated and the residue purified by crystallization, yielding the title compound (1.09 g, yield 61%; m.p. 448–449 K). Crystals suitable for X-ray analysis were obtained by slow evaporation of an aqueous solution at 288 K.

Refinement

Carbon bound H atoms were placed geometrically and treated as riding on their carriers, with methylene C—H distance of 0.97 Å, aromatic C—H of 0.93 Å and Uiso(H) = 1.2Ueq(C). H atoms from hydroxyl groups were refined with the distance restraint of O—H = 0.82 (2) Å and Uiso(H) = 1.5 Ueq(O)..

Figures

Fig. 1.
View of the title molecule showing the atom-labelling scheme; displacement ellipsoids are shown at the 30% probability level (symmetry code to generate atoms with the label A: 2-x, 1-y, 1-z)
Fig. 2.
Crystal packing of the title compound viewed down the b direction. Dashed lines indicate hydrogen bonds.

Crystal data

C14H22O4Dx = 1.256 Mg m3
Mr = 254.32Melting point = 448–449 K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2317 reflections
a = 9.939 (6) Åθ = 2.6–27.1°
b = 8.803 (5) ŵ = 0.09 mm1
c = 15.366 (9) ÅT = 291 K
V = 1344.5 (14) Å3Block, colourless
Z = 40.30 × 0.24 × 0.22 mm
F(000) = 552

Data collection

Bruker SMART APEX CCD diffractometer1636 independent reflections
Radiation source: sealed tube1215 reflections with I > 2σ(I)
graphiteRint = 0.057
[var phi] and ω scansθmax = 28.3°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)h = −5→13
Tmin = 0.97, Tmax = 0.98k = −11→11
7571 measured reflectionsl = −20→20

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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.08w = 1/[σ2(Fo2) + (0.06P)2] where P = (Fo2 + 2Fc2)/3
1636 reflections(Δ/σ)max < 0.001
88 parametersΔρmax = 0.19 e Å3
2 restraintsΔρmin = −0.17 e Å3

Special details

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)

xyzUiso*/Ueq
C11.09492 (13)0.40412 (13)0.53366 (8)0.0388 (3)
H11.16000.34020.55720.047*
C21.09178 (14)0.55517 (13)0.55850 (8)0.0396 (3)
H21.15480.59100.59820.048*
C30.99643 (11)0.65355 (12)0.52522 (8)0.0316 (3)
C40.99230 (13)0.81711 (12)0.55423 (8)0.0347 (3)
H4A0.92880.87190.51800.042*
H4B1.08040.86200.54540.042*
C50.95220 (12)0.83713 (12)0.64958 (7)0.0303 (3)
H51.00450.76460.68420.036*
C60.98372 (12)0.99558 (14)0.68286 (9)0.0371 (3)
H6A0.93691.06940.64710.045*
H6B0.95021.00530.74190.045*
C70.80474 (13)0.80040 (14)0.66200 (8)0.0399 (3)
H7A0.75120.87770.63330.048*
H7B0.78530.70390.63420.048*
O11.12348 (9)1.02918 (10)0.68214 (6)0.0417 (3)
H1A1.1656 (18)0.9562 (18)0.7010 (10)0.063*
O20.76614 (10)0.79212 (10)0.75078 (6)0.0471 (3)
H2A0.8000 (18)0.7167 (18)0.7731 (12)0.071*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0425 (7)0.0340 (7)0.0399 (7)0.0101 (5)−0.0108 (5)−0.0035 (5)
C20.0430 (7)0.0361 (7)0.0398 (7)0.0027 (5)−0.0128 (6)−0.0076 (5)
C30.0383 (7)0.0269 (6)0.0297 (6)0.0000 (5)0.0018 (5)−0.0016 (4)
C40.0434 (7)0.0249 (6)0.0357 (7)−0.0014 (5)0.0023 (5)0.0003 (5)
C50.0335 (6)0.0231 (5)0.0343 (6)0.0006 (4)0.0004 (5)−0.0012 (4)
C60.0384 (7)0.0287 (6)0.0443 (8)0.0004 (5)0.0028 (6)−0.0077 (5)
C70.0375 (7)0.0363 (6)0.0460 (7)−0.0018 (5)0.0032 (6)−0.0002 (5)
O10.0390 (5)0.0296 (5)0.0564 (6)−0.0040 (4)−0.0023 (4)−0.0028 (4)
O20.0485 (6)0.0379 (5)0.0550 (6)0.0090 (4)0.0188 (5)0.0089 (4)

Geometric parameters (Å, °)

C1—C3i1.3787 (17)C5—C61.5183 (17)
C1—C21.3838 (17)C5—H50.9800
C1—H10.9300C6—O11.4203 (18)
C2—C31.3819 (17)C6—H6A0.9700
C2—H20.9300C6—H6B0.9700
C3—C41.5078 (18)C7—O21.4190 (18)
C4—C51.5285 (18)C7—H7A0.9700
C4—H4A0.9700C7—H7B0.9700
C4—H4B0.9700O1—H1A0.820 (16)
C5—C71.513 (2)O2—H2A0.820 (17)
C3i—C1—C2121.33 (11)C7—C5—H5107.8
C3i—C1—H1119.3C6—C5—H5107.8
C2—C1—H1119.3C4—C5—H5107.8
C3—C2—C1121.04 (12)O1—C6—C5112.98 (10)
C3—C2—H2119.5O1—C6—H6A109.0
C1—C2—H2119.5C5—C6—H6A109.0
C1i—C3—C2117.63 (11)O1—C6—H6B109.0
C1i—C3—C4121.85 (11)C5—C6—H6B109.0
C2—C3—C4120.51 (11)H6A—C6—H6B107.8
C3—C4—C5113.62 (10)O2—C7—C5113.21 (11)
C3—C4—H4A108.8O2—C7—H7A108.9
C5—C4—H4A108.8C5—C7—H7A108.9
C3—C4—H4B108.8O2—C7—H7B108.9
C5—C4—H4B108.8C5—C7—H7B108.9
H4A—C4—H4B107.7H7A—C7—H7B107.7
C7—C5—C6110.72 (10)C6—O1—H1A109.5 (12)
C7—C5—C4110.41 (10)C7—O2—H2A109.5 (12)
C6—C5—C4112.03 (10)
C3i—C1—C2—C30.2 (2)C3—C4—C5—C6165.14 (10)
C1—C2—C3—C1i−0.2 (2)C7—C5—C6—O1173.08 (10)
C1—C2—C3—C4178.72 (12)C4—C5—C6—O1−63.19 (14)
C1i—C3—C4—C5111.75 (15)C6—C5—C7—O2−65.22 (13)
C2—C3—C4—C5−67.11 (15)C4—C5—C7—O2170.13 (9)
C3—C4—C5—C7−70.96 (13)

Symmetry codes: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1A···O2ii0.820 (16)1.906 (17)2.7254 (17)177.4 (17)
O2—H2A···O1iii0.820 (17)1.943 (17)2.7612 (17)175.5 (17)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2172).

References

  • Bruker (2000). SMART, SAINT and SADABS Bruker AXS Inc. Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Xi, H., Gao, Y., Sun, X., Meng, Q. & Jiang, Y. (2008). Acta Cryst. E64, o1853. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography