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

Gao, Y.; Xi, H.; Sun, X.; Fu, Y.; Liu, L.

doi:10.1107/S1600536808041688

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o170

doi:10.1107/S1600536808041688

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

Yajun Gao,^a Haitao Xi,^a Xiaoqiang Sun,^a ^* Yongsheng Fu ^a and Li Liu ^a

^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 ).

Experimental

Crystal data

C₁₄H₂₂O₄
M_r = 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 ) 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[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
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

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

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

checkCIF report

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.

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

	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.

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

Crystal data top

C₁₄H₂₂O₄	D_x = 1.256 Mg m⁻³
M_r = 254.32	Melting point = 448–449 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2317 reflections
a = 9.939 (6) Å	θ = 2.6–27.1°
b = 8.803 (5) Å	µ = 0.09 mm⁻¹
c = 15.366 (9) Å	T = 291 K
V = 1344.5 (14) Å³	Block, colourless
Z = 4	0.30 × 0.24 × 0.22 mm
F(000) = 552

Data collection top

Bruker SMART APEX CCD diffractometer	1636 independent reflections
Radiation source: sealed tube	1215 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −5→13
T_min = 0.97, T_max = 0.98	k = −11→11
7571 measured reflections	l = −20→20

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.06P)²] where P = (F_o² + 2F_c²)/3
1636 reflections	(Δ/σ)_max < 0.001
88 parameters	Δρ_max = 0.19 e Å⁻³
2 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₄H₂₂O₄	V = 1344.5 (14) Å³
M_r = 254.32	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 9.939 (6) Å	µ = 0.09 mm⁻¹
b = 8.803 (5) Å	T = 291 K
c = 15.366 (9) Å	0.30 × 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)
T_min = 0.97, T_max = 0.98	R_int = 0.057
7571 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	2 restraints
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.19 e Å⁻³
1636 reflections	Δρ_min = −0.17 e Å⁻³
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

	x	y	z	U_iso*/U_eq
C1	1.09492 (13)	0.40412 (13)	0.53366 (8)	0.0388 (3)
H1	1.1600	0.3402	0.5572	0.047*
C2	1.09178 (14)	0.55517 (13)	0.55850 (8)	0.0396 (3)
H2	1.1548	0.5910	0.5982	0.048*
C3	0.99643 (11)	0.65355 (12)	0.52522 (8)	0.0316 (3)
C4	0.99230 (13)	0.81711 (12)	0.55423 (8)	0.0347 (3)
H4A	0.9288	0.8719	0.5180	0.042*
H4B	1.0804	0.8620	0.5454	0.042*
C5	0.95220 (12)	0.83713 (12)	0.64958 (7)	0.0303 (3)
H5	1.0045	0.7646	0.6842	0.036*
C6	0.98372 (12)	0.99558 (14)	0.68286 (9)	0.0371 (3)
H6A	0.9369	1.0694	0.6471	0.045*
H6B	0.9502	1.0053	0.7419	0.045*
C7	0.80474 (13)	0.80040 (14)	0.66200 (8)	0.0399 (3)
H7A	0.7512	0.8777	0.6333	0.048*
H7B	0.7853	0.7039	0.6342	0.048*
O1	1.12348 (9)	1.02918 (10)	0.68214 (6)	0.0417 (3)
H1A	1.1656 (18)	0.9562 (18)	0.7010 (10)	0.063*
O2	0.76614 (10)	0.79212 (10)	0.75078 (6)	0.0471 (3)
H2A	0.8000 (18)	0.7167 (18)	0.7731 (12)	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0425 (7)	0.0340 (7)	0.0399 (7)	0.0101 (5)	−0.0108 (5)	−0.0035 (5)
C2	0.0430 (7)	0.0361 (7)	0.0398 (7)	0.0027 (5)	−0.0128 (6)	−0.0076 (5)
C3	0.0383 (7)	0.0269 (6)	0.0297 (6)	0.0000 (5)	0.0018 (5)	−0.0016 (4)
C4	0.0434 (7)	0.0249 (6)	0.0357 (7)	−0.0014 (5)	0.0023 (5)	0.0003 (5)
C5	0.0335 (6)	0.0231 (5)	0.0343 (6)	0.0006 (4)	0.0004 (5)	−0.0012 (4)
C6	0.0384 (7)	0.0287 (6)	0.0443 (8)	0.0004 (5)	0.0028 (6)	−0.0077 (5)
C7	0.0375 (7)	0.0363 (6)	0.0460 (7)	−0.0018 (5)	0.0032 (6)	−0.0002 (5)
O1	0.0390 (5)	0.0296 (5)	0.0564 (6)	−0.0040 (4)	−0.0023 (4)	−0.0028 (4)
O2	0.0485 (6)	0.0379 (5)	0.0550 (6)	0.0090 (4)	0.0188 (5)	0.0089 (4)

Geometric parameters (Å, º) top

C1—C3ⁱ	1.3787 (17)	C5—C6	1.5183 (17)
C1—C2	1.3838 (17)	C5—H5	0.9800
C1—H1	0.9300	C6—O1	1.4203 (18)
C2—C3	1.3819 (17)	C6—H6A	0.9700
C2—H2	0.9300	C6—H6B	0.9700
C3—C4	1.5078 (18)	C7—O2	1.4190 (18)
C4—C5	1.5285 (18)	C7—H7A	0.9700
C4—H4A	0.9700	C7—H7B	0.9700
C4—H4B	0.9700	O1—H1A	0.820 (16)
C5—C7	1.513 (2)	O2—H2A	0.820 (17)

C3ⁱ—C1—C2	121.33 (11)	C7—C5—H5	107.8
C3ⁱ—C1—H1	119.3	C6—C5—H5	107.8
C2—C1—H1	119.3	C4—C5—H5	107.8
C3—C2—C1	121.04 (12)	O1—C6—C5	112.98 (10)
C3—C2—H2	119.5	O1—C6—H6A	109.0
C1—C2—H2	119.5	C5—C6—H6A	109.0
C1ⁱ—C3—C2	117.63 (11)	O1—C6—H6B	109.0
C1ⁱ—C3—C4	121.85 (11)	C5—C6—H6B	109.0
C2—C3—C4	120.51 (11)	H6A—C6—H6B	107.8
C3—C4—C5	113.62 (10)	O2—C7—C5	113.21 (11)
C3—C4—H4A	108.8	O2—C7—H7A	108.9
C5—C4—H4A	108.8	C5—C7—H7A	108.9
C3—C4—H4B	108.8	O2—C7—H7B	108.9
C5—C4—H4B	108.8	C5—C7—H7B	108.9
H4A—C4—H4B	107.7	H7A—C7—H7B	107.7
C7—C5—C6	110.72 (10)	C6—O1—H1A	109.5 (12)
C7—C5—C4	110.41 (10)	C7—O2—H2A	109.5 (12)
C6—C5—C4	112.03 (10)

C3ⁱ—C1—C2—C3	0.2 (2)	C3—C4—C5—C6	165.14 (10)
C1—C2—C3—C1ⁱ	−0.2 (2)	C7—C5—C6—O1	173.08 (10)
C1—C2—C3—C4	178.72 (12)	C4—C5—C6—O1	−63.19 (14)
C1ⁱ—C3—C4—C5	111.75 (15)	C6—C5—C7—O2	−65.22 (13)
C2—C3—C4—C5	−67.11 (15)	C4—C5—C7—O2	170.13 (9)
C3—C4—C5—C7	−70.96 (13)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2ⁱⁱ	0.820 (16)	1.906 (17)	2.7254 (17)	177.4 (17)
O2—H2A···O1ⁱⁱⁱ	0.820 (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.

Experimental details

Crystal data
Chemical formula	C₁₄H₂₂O₄
M_r	254.32
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	291
a, b, c (Å)	9.939 (6), 8.803 (5), 15.366 (9)
V (Å³)	1344.5 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.24 × 0.22

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.97, 0.98
No. of measured, independent and observed [I > 2σ(I)] reflections	7571, 1636, 1215
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.115, 1.08
No. of reflections	1636
No. of parameters	88
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.17

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+1/2, y, −z+3/2; (ii) −x+2, y−1/2, −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

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