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ISSN: 2056-9890

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

aSchool of Chemistry and Chemical Engineering, Jiangsu Polytechnic University, Changzhou 213164, People's Republic of China
*Correspondence e-mail: xiaoqiang_sun@yahoo.com.cn

(Received 11 October 2008; accepted 9 December 2008; online 20 December 2008)

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[Xi, H., Gao, Y., Sun, X., Meng, Q. & Jiang, Y. (2008). Acta Cryst. E64, o1853.]).

[Scheme 1]

Experimental

Crystal data
  • C14H22O4

  • Mr = 254.32

  • Orthorhombic, P b c a

  • 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[Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA.]) Tmin = 0.97, Tmax = 0.98

  • 7571 measured reflections

  • 1636 independent reflections

  • 1215 reflections with I > 2σ(I)

  • Rint = 0.057

Refinement
  • R[F2 > 2σ(F2)] = 0.038

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1A⋯O2i 0.820 (16) 1.906 (17) 2.7254 (17) 177.4 (17)
O2—H2A⋯O1ii 0.820 (17) 1.943 (17) 2.7612 (17) 175.5 (17)
Symmetry codes: (i) [x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]; (ii) [-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}].

Data collection: SMART (Bruker, 2000[Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2000[Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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).

Related literature top

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

Experimental top

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 top

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)..

Computing details top

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

Figures top
[Figure 1] 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)
[Figure 2] Fig. 2. Crystal packing of the title compound viewed down the b direction. Dashed lines indicate hydrogen bonds.
2,2'-(p-Phenylenedimethylene)bis(propane-1,3-diol) top
Crystal data top
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 top
Bruker SMART APEX CCD
diffractometer
1636 independent reflections
Radiation source: sealed tube1215 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
ϕ and ω scansθmax = 28.3°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 513
Tmin = 0.97, Tmax = 0.98k = 1111
7571 measured reflectionsl = 2020
Refinement top
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 = 1.08 w = 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
Crystal data top
C14H22O4V = 1344.5 (14) Å3
Mr = 254.32Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 9.939 (6) ŵ = 0.09 mm1
b = 8.803 (5) ÅT = 291 K
c = 15.366 (9) Å0.30 × 0.24 × 0.22 mm
Data collection top
Bruker SMART APEX CCD
diffractometer
1636 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
1215 reflections with I > 2σ(I)
Tmin = 0.97, Tmax = 0.98Rint = 0.057
7571 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0382 restraints
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.19 e Å3
1636 reflectionsΔρmin = 0.17 e Å3
88 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
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) top
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, º) top
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—C1i0.2 (2)C7—C5—C6—O1173.08 (10)
C1—C2—C3—C4178.72 (12)C4—C5—C6—O163.19 (14)
C1i—C3—C4—C5111.75 (15)C6—C5—C7—O265.22 (13)
C2—C3—C4—C567.11 (15)C4—C5—C7—O2170.13 (9)
C3—C4—C5—C770.96 (13)
Symmetry code: (i) x+2, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
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, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC14H22O4
Mr254.32
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)291
a, b, c (Å)9.939 (6), 8.803 (5), 15.366 (9)
V3)1344.5 (14)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.30 × 0.24 × 0.22
Data collection
DiffractometerBruker SMART APEX CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.97, 0.98
No. of measured, independent and
observed [I > 2σ(I)] reflections
7571, 1636, 1215
Rint0.057
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.115, 1.08
No. of reflections1636
No. of parameters88
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.19, 0.17

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O2i0.820 (16)1.906 (17)2.7254 (17)177.4 (17)
O2—H2A···O1ii0.820 (17)1.943 (17)2.7612 (17)175.5 (17)
Symmetry codes: (i) x+1/2, y, z+3/2; (ii) x+2, y1/2, z+3/2.
 

Acknowledgements

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.

References

First citationBruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationXi, H., Gao, Y., Sun, X., Meng, Q. & Jiang, Y. (2008). Acta Cryst. E64, o1853.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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ISSN: 2056-9890
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