3 (2 Meth­oxy­phen­­oxy)propane 1,2 diol

organic papers

Acta Cryst.(2005). E61, o1999–o2000 doi:10.1107/S1600536805016909 Wanget al. _C

10H14O4

o1999

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

3-(2-Methoxyphenoxy)propane-1,2-diol

Yongli Wang, Ming Li,* Lijun Liu, Lina Zhou and Jingkang Wang

School of Chemical Engineering and

Technology, Tianjin University, Tianjin 300072, People’s Republic of China

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C–C) = 0.003 A˚

Rfactor = 0.048

wRfactor = 0.148

Data-to-parameter ratio = 17.7

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography Printed in Great Britain – all rights reserved

The title compound, C10H14O4, is used to cure coughs and

clear up phlegm and it is also used as an intermediate in the synthesis of other medicinal products. The entire molecule, except for atoms C10 and O4, is essentially planar (to within 0.001 A˚ ).

Comment

The title compound, (I), also known as guaiphenesin, is an ingredient usually found in cold preparations. In the year 1530, it was first extracted from guaiacum and used to treat rheu-matism. Over 20 years ago, it was synthesized, named guai-phenesin, and pressed into tablets (Starlanyl, 2001). To the best of our knowledge [using Chemical Abstracts and the Cambridge Structural Database (Allen, 2002)], the single-crystal structure has not been reported previously.

The molecular structure of (I) is shown in Fig. 1. It can be seen that the entire molecule, except for atoms C10 and O4

Received 14 April 2005 Accepted 26 May 2005 Online 10 June 2005

Figure 1

and the H atoms, is essentially planar (to within 0.001 A˚ ). The crystal packing projected on to theacface is shown in Fig. 2. There are two kinds of intermolecular hydrogen bonds between molecules (Table 1). The hydrogen bond O3— H3 O4 is approximately parallel to theacface, while O4— H4 O3 is approximately perpendicular to theacface.

Experimental

The title compound was provided by Tianjin Zhongxin Pharmaceu-tical Co. Ltd. A saturated solution of guaiphenesin in ethanol was prepared at 338–343 K and then a small quantity of seeds was added when the temperature fell to 308 K. After a long time, a large quantity of white crystals was obtained by recrystallization. The product was characterized by NMR, IR and elemental analyses, and its purity was 99%. The melting point determined by DSC (differ-ential scanning calorimetry) is 355.4 K. Colorless block-shaped single crystals suitable for X-ray diffraction were obtained by adding a small quantity of seeds to a room-temperature solution of the above product and placing it in a refrigerator for 3 d.

Crystal data

C10H14O4 Mr= 198.21

Orthorhombic,P212121 a= 4.9836 (10) A˚ b= 7.6562 (15) A˚ c= 25.698 (5) A˚ V= 980.5 (3) A˚3 Z= 4

Dx= 1.343 Mg m 3 MoKradiation Cell parameters from 9593

reflections = 3.1–27.5

= 0.10 mm1 T= 293 (2) K Block, colorless

0.380.200.09 mm

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer !scans

Absorption correction: multi-scan (ABSCOR; Higashi, 1995) Tmin= 0.962,Tmax= 0.991 9631 measured reflections

2248 independent reflections 1862 reflections withI> 2(I) Rint= 0.092

max= 27.5

h=6!6 k=9!9 l=33!32

Refinement

Refinement onF2 R[F2_{> 2(F}2_{)] = 0.048} wR(F2_{) = 0.148} S= 1.00 2248 reflections 127 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0903P)2 + 0.0695P]

whereP= (Fo2+ 2Fc2)/3 (/)max= 0.001

max= 0.31 e A˚3 min=0.42 e A˚3

Table 1

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

O3—H3B O4i 0.82 1.96 2.744 (2) 161 O4—H4C O3ii

0.82 1.99 2.729 (2) 149

Symmetry codes: (i)xþ1;y1 2;zþ

1

2; (ii)xþ1;y;z.

H atoms were placed in calculated positions and constrained to ride on their parent atoms, with C—H = 0.93–0.98 A˚ andUiso(H) =

1.2Ueq(C). In the absence of significant anomalous dispersion effects,

Friedel equivalents were merged prior to the final refinements, and the absolute configuration was assigned to correspond with the known chiral centers of the precursor molecule, which remained unchanged during the synthesis of the title compound.

Data collection:RAPID-AUTO (Rigaku, 2001); cell refinement:

RAPID-AUTO; data reduction:RAPID-AUTO; program(s) used to solve structure: SHELXS97(Sheldrick, 1997); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics:

ORTEPII (Johnson, 1976); software used to prepare material for publication:SHELXL97.

The authors gratefully acknowledge support from the SRCICT of Tianjin University and the materials afforded by Tianjin Zhongxin Pharmaceutical Co. Ltd.

References

Allen, F. H. (2002).Acta Cryst.B58, 380–388.

Higashi, T. (1995).ABSCOR. Rigaku Corporation, Tokyo, Japan.

Johnson, C. K. (1976).ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.

Rigaku (2001).RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of

Go¨ttingen, Germany.

Starlanyl, D. J. (2001).Fibromyalgia and Chronic Myofascial Pain: A Survival Manual, 2nd ed., p. 201. Oakland: New Harbinger.

Figure 2

supporting information

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Acta Cryst. (2005). E61, o1999–o2000

supporting information

Acta Cryst. (2005). E61, o1999–o2000 [https://doi.org/10.1107/S1600536805016909]

3-(2-Methoxyphenoxy)propane-1,2-diol

Yongli Wang, Ming Li, Lijun Liu, Lina Zhou and Jingkang Wang

3-(2-Methoxyphenoxy)propane-1,2-diol

Crystal data

C10H14O4 Mr = 198.21

Orthorhombic, P212121

a = 4.9836 (10) Å

b = 7.6562 (15) Å

c = 25.698 (5) Å

V = 980.5 (3) Å3

Z = 4

F(000) = 424

Dx = 1.343 Mg m−3

Melting point: 355.4 K

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 9631 reflections

θ = 3.1–27.5°

µ = 0.10 mm−1

T = 293 K

Needle, colorless 0.38 × 0.20 × 0.09 mm

Data collection

Rigaku R-axis Rapid IP area-detector diffractometer

Radiation source: rotating anode Graphite monochromator Oscillation scans

Absorption correction: multi-scan (ABSCOR; Higashi, 1995) Tmin = 0.962, Tmax = 0.991

9593 measured reflections 2248 independent reflections 1862 reflections with I > 2σ(I) Rint = 0.092

θmax = 27.5°, θmin = 3.1°

h = −6→6

k = −9→9

l = −33→32

Refinement

Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.048} wR(F2_{) = 0.148}

S = 1.00

2248 reflections 127 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained w = 1/[σ2_(F

o2) + (0.0903P)2 + 0.0695P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001

Δρmax = 0.31 e Å−3

Δρmin = −0.42 e Å−3

Special details

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

C1 1.2993 (5) 0.5757 (4) 0.02231 (11) 0.0575 (7)

H1A 1.2735 0.6945 0.0115 0.086*

H1B 1.3004 0.5009 −0.0077 0.086*

H1C 1.4674 0.5655 0.0403 0.086*

C2 1.0968 (4) 0.3583 (3) 0.07477 (8) 0.0361 (4)

C3 1.2737 (5) 0.2306 (3) 0.05803 (8) 0.0450 (5)

H3A 1.3976 0.2562 0.0321 0.054*

C4 1.2676 (5) 0.0650 (3) 0.07965 (10) 0.0497 (6)

H4A 1.3853 −0.0203 0.0677 0.060*

C5 1.0883 (5) 0.0258 (3) 0.11871 (11) 0.0483 (6)

H5A 1.0859 −0.0855 0.1332 0.058*

C6 0.9106 (5) 0.1529 (3) 0.13648 (9) 0.0409 (5)

H6A 0.7896 0.1264 0.1629 0.049*

C7 0.9138 (4) 0.3183 (3) 0.11489 (7) 0.0339 (4)

C8 0.5792 (4) 0.4210 (3) 0.17351 (8) 0.0348 (4)

H8A 0.6862 0.3980 0.2043 0.042*

H8B 0.4656 0.3204 0.1670 0.042*

C9 0.4095 (4) 0.5827 (3) 0.18138 (7) 0.0319 (4)

H9A 0.2902 0.5954 0.1513 0.038*

C10 0.5733 (4) 0.7480 (3) 0.18666 (9) 0.0395 (5)

H10A 0.6559 0.7752 0.1535 0.047*

H10B 0.4554 0.8441 0.1958 0.047*

O1 1.0869 (3) 0.5255 (2) 0.05609 (6) 0.0469 (4)

O2 0.7492 (3) 0.45292 (19) 0.12978 (6) 0.0394 (4)

O3 0.2484 (3) 0.5507 (2) 0.22650 (6) 0.0406 (4)

H3B 0.2657 0.4485 0.2355 0.061*

O4 0.7766 (3) 0.7314 (2) 0.22526 (7) 0.0499 (4)

H4C 0.8962 0.6676 0.2144 0.075*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

C1 0.0508 (13) 0.0691 (19) 0.0527 (14) −0.0041 (13) 0.0085 (11) 0.0197 (13)

C2 0.0337 (10) 0.0410 (11) 0.0336 (9) −0.0013 (9) −0.0008 (9) −0.0026 (8)

C3 0.0392 (11) 0.0528 (14) 0.0432 (12) 0.0021 (11) 0.0050 (10) −0.0095 (10)

C4 0.0380 (11) 0.0470 (14) 0.0643 (15) 0.0119 (11) 0.0007 (12) −0.0128 (11)

C5 0.0398 (11) 0.0368 (12) 0.0684 (14) 0.0045 (10) −0.0046 (12) 0.0005 (10)

C6 0.0340 (9) 0.0383 (12) 0.0505 (12) −0.0002 (10) 0.0023 (10) −0.0011 (9)

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Acta Cryst. (2005). E61, o1999–o2000

C8 0.0313 (9) 0.0362 (11) 0.0370 (10) 0.0012 (9) 0.0029 (8) −0.0020 (8)

C9 0.0295 (9) 0.0328 (10) 0.0335 (9) 0.0028 (8) −0.0010 (8) 0.0016 (8)

C10 0.0348 (9) 0.0357 (11) 0.0480 (11) 0.0010 (10) −0.0002 (10) 0.0009 (9)

O1 0.0460 (8) 0.0486 (10) 0.0462 (8) 0.0021 (8) 0.0115 (8) 0.0087 (7)

O2 0.0408 (7) 0.0353 (8) 0.0420 (8) 0.0051 (7) 0.0102 (7) 0.0022 (6)

O3 0.0369 (7) 0.0400 (9) 0.0450 (8) 0.0080 (7) 0.0089 (7) 0.0098 (6)

O4 0.0340 (7) 0.0476 (10) 0.0682 (10) 0.0102 (7) −0.0105 (7) −0.0186 (8)

Geometric parameters (Å, º)

C1—O1 1.422 (3) C6—H6A 0.9300

C1—H1A 0.9600 C7—O2 1.372 (2)

C1—H1B 0.9600 C8—O2 1.428 (2)

C1—H1C 0.9600 C8—C9 1.513 (3)

C2—O1 1.368 (3) C8—H8A 0.9700

C2—C3 1.385 (3) C8—H8B 0.9700

C2—C7 1.410 (3) C9—O3 1.431 (2)

C3—C4 1.384 (4) C9—C10 1.512 (3)

C3—H3A 0.9300 C9—H9A 0.9800

C4—C5 1.377 (4) C10—O4 1.424 (3)

C4—H4A 0.9300 C10—H10A 0.9700

C5—C6 1.393 (3) C10—H10B 0.9700

C5—H5A 0.9300 O3—H3B 0.8200

C6—C7 1.383 (3) O4—H4C 0.8200

O1—C1—H1A 109.5 C6—C7—C2 120.0 (2)

O1—C1—H1B 109.5 O2—C8—C9 107.24 (16)

H1A—C1—H1B 109.5 O2—C8—H8A 110.3

O1—C1—H1C 109.5 C9—C8—H8A 110.3

H1A—C1—H1C 109.5 O2—C8—H8B 110.3

H1B—C1—H1C 109.5 C9—C8—H8B 110.3

O1—C2—C3 125.1 (2) H8A—C8—H8B 108.5

O1—C2—C7 115.88 (18) O3—C9—C10 111.92 (16)

C3—C2—C7 119.0 (2) O3—C9—C8 106.34 (15)

C4—C3—C2 120.5 (2) C10—C9—C8 113.31 (16)

C4—C3—H3A 119.7 O3—C9—H9A 108.4

C2—C3—H3A 119.7 C10—C9—H9A 108.4

C5—C4—C3 120.4 (2) C8—C9—H9A 108.4

C5—C4—H4A 119.8 O4—C10—C9 111.82 (18)

C3—C4—H4A 119.8 O4—C10—H10A 109.3

C4—C5—C6 120.0 (2) C9—C10—H10A 109.3

C4—C5—H5A 120.0 O4—C10—H10B 109.3

C6—C5—H5A 120.0 C9—C10—H10B 109.3

C7—C6—C5 120.1 (2) H10A—C10—H10B 107.9

C7—C6—H6A 120.0 C2—O1—C1 116.11 (19)

C5—C6—H6A 120.0 C7—O2—C8 116.46 (16)

O2—C7—C6 124.70 (19) C9—O3—H3B 109.5

O1—C2—C3—C4 179.8 (2) C3—C2—C7—C6 −0.8 (3)

C7—C2—C3—C4 1.2 (3) O2—C8—C9—O3 −177.81 (14)

C2—C3—C4—C5 −1.0 (4) O2—C8—C9—C10 −54.4 (2)

C3—C4—C5—C6 0.4 (4) O3—C9—C10—O4 68.2 (2)

C4—C5—C6—C7 0.1 (4) C8—C9—C10—O4 −52.0 (2)

C5—C6—C7—O2 −179.5 (2) C3—C2—O1—C1 −9.1 (3)

C5—C6—C7—C2 0.1 (3) C7—C2—O1—C1 169.5 (2)

O1—C2—C7—O2 0.2 (3) C6—C7—O2—C8 5.2 (3)

C3—C2—C7—O2 178.88 (18) C2—C7—O2—C8 −174.42 (16)

O1—C2—C7—C6 −179.51 (19) C9—C8—O2—C7 −177.72 (16)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O3—H3B···O4i _{0.82 1.96 2.744 (2) 161}

O4—H4C···O3ii _{0.82 1.99 2.729 (2) 149}