Acta Cryst.(2003). E59, o1089±o1091 DOI: 10.1107/S1600536803014223 Doyle Britton C12H18O2
o1089
organic papers
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
Durenedimethanol
Doyle Britton
Department of Chemistry, University of Minnesota, Minneapolis, MN 55455, USA
Correspondence e-mail: [email protected]
Key indicators Single-crystal X-ray study T= 174 K
Mean(C±C) = 0.002 AÊ Rfactor = 0.043 wRfactor = 0.104
Data-to-parameter ratio = 14.1
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2003 International Union of Crystallography Printed in Great Britain ± all rights reserved
Durenedimethanol (2,3,5,6-tetramethyl-1,4-phenylenedimeth-anol), C12H18O2, crystallizes in space groupI41/a with a
three-dimensional structure held together by OÐH O hydrogen
bonds. The hydrogen bonds have a fourfold helical arrange-ment. The molecule lies on a crystallographic center of symmetry.
Comment
Shan & Jones (2001) have reported the structure of 1,4-benzenedimethanol, a molecule of potential use in crystal engineering. The structure of the durene analog, durenedi-methanol, (I), is reported here.
The labeling and the anisotropic displacement parameters are shown in Fig. 1. The molecule lies on a crystallographic center of symmetry. The bond lengths and angles are normal. The ring is planar within experimental error [displacements (AÊ): C1 ÿ0.001 (1), C2 0.001 (1), C3 0.001 (1)], but the substituents are distinctly puckered [displacements: C4
ÿ0.108 (1), C5 0.108 (1), C6ÿ0.052 (1)]. These displacements are similar to those in hexamethylbenzene (Le MagueÁReset al., 2001).
The packing is shown in Fig. 2. A 41screw axis of hydrogen
bonds can be clearly seen. The distances and angles in the hydrogen bonds are given in Table 1, where they are compared with those in benzenedimethanol (Shan & Jones, 2001) and benzenediisopropanol (KoritsaÂnszky & Menczel, 1982). All of the individual hydrogen-bond parameters in durenedi-methanol and benzenedidurenedi-methanol are virtually identical. The
benzenediisopropanol has OÐH O angles that are further
from linear and slightly longer O O distances. For discus-sions of hydrogen bonding in alcohols, see Brock & Duncan (1994) and Brock (2002).
The packings in the three structures are quite different. In all three, the graph sets (Etter et al., 1990; Bernstein et al., 1995) for the dominant interactions are the same,C(2), if we consider all chemically equivalent OH groups to be the same. However, in benzenedimethanol adjacent OH groups in the chain are crystallographically independent so that an alter-native description would be C22(4); together they form a
pseudo-twofold screw axis. In benzenediisopropanol three adjacent OH groups in the chain are crystallographically
organic papers
o1090
Doyle Britton C12H18O2 Acta Cryst.(2003). E59, o1089±o1091independent and the alternative description would beC33(6);
together they form a pseudo-threefold screw axis. In durenedimethanol there is only one OH in the asymmetric unit, which is involved in interactions via a crystallographic fourfold screw axis.
If we return to considering the chemically equivalent OH groups the same, so that the basic graph sets are the same, the complex graph sets show the differences clearly: benzenedi-methanol C(2)[C(9)][R44(22)], benzenediisopropanol C
(2)-[C(9)][R22(18)][R66(26)] and durenedimethanolC(2)[R44(36). In
the ®rst two, the overall hydrogen bonding leads to two-dimensional networks, while in durenedimethanol it leads to a three-dimensional network.
Finally, it should be noted that durenedimethanol and its
isomer dimethoxydurene (Wieczorek et al., 1975) have the
same molecular volumes within experimental error despite the great differences in their intermolecular interactions and packing.
Experimental
The compound was obtained from the Shell Development Co. Satisfactory crystals grew as prisms from ethanol.
Crystal data C12H18O2
Mr= 194.26
Tetragonal,I41=a
a= 16.042 (4) AÊ
c= 8.656 (2) AÊ
V= 2227.6 (9) AÊ3
Z= 8
Dx= 1.159 Mg mÿ3
MoKradiation Cell parameters from 3471
re¯ections
= 2.5±25.0
= 0.08 mmÿ1
T= 174 (2) K Prism, colorless 0.380.220.22 mm Data collection
Siemens SMART area-detector diffractometer
!scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995)
Tmin= 0.97,Tmax= 0.98 5239 measured re¯ections
990 independent re¯ections 871 re¯ections withI> 2(I)
Rint= 0.025 max= 25.1
h=ÿ19!13
k=ÿ18!19
l=ÿ10!9
Re®nement Re®nement onF2
R[F2> 2(F2)] = 0.043
wR(F2) = 0.104
S= 1.13 990 re¯ections 70 parameters
H atoms treated by a mixture of independent and constrained re®nement
w= 1/[2(F
o2) + (0.04P)2
+ 1.83P]
whereP= (Fo2+ 2Fc2)/3
(/)max= 0.001 max= 0.16 e AÊÿ3 min=ÿ0.16 e AÊÿ3
Table 1
Distances and angles (AÊ,) in the OÐH O hydrogen bonds.
O H O OÐH OÐH O H O H OÐC C O Ref.
O1 H1 O1i 0.87 (2) 175 (2) 1.85 (2) 120 (2) 2.717 (2) a O1 H1 O2 0.90 (3) 174 (2) 1.82 (3) 119 (2) 2.714 (2) b
O2 H2 O1 0.92 (2) 170 (2) 1.81 (3) 123 (2) 2.725 (2) b
O1 H1 O3 1.07 (4) 155 (3) 1.75 (4) 124 (3) 2.757 (4) c
O3 H3 O2 0.97 (4) 161 (3) 1.84 (4) 125 (3) 2.779 (4) c
O2 H2 H1 0.97 (4) 156 (3) 1.93 (4) 124 (3) 2.848 (4) c
Symmetry code: (i)3
4ÿy;14x;14z. References: (a) durenedimethanol (this work); (b)
benzenedimethanol (Shan & Jones, 2001); (c) benzenediisopropanol (KoritsaÂnszky & Menczel, 1982).
The methyl and methylene H atoms were included at idealized positions, with the methyl groups allowed to rotate around the CÐC bonds. The hydroxy H atom was re®ned with an isotropic displace-ment parameter. The CÐH distances were ®xed at 0.99 AÊ for methylene and 0.98 AÊ for methyl H atoms. The isotropic displace-ment parameters for both were ®xed at 1.5 times theUeqvalue of the attached C atom.
Data collection:SMART(Siemens, 1995); cell re®nement:SAINT
(Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1994); program(s) used to re®ne structure:SHELXTL; molecular graphics:SHELXTL; software used to prepare material for publication:SHELXTL.
References
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995).Angew. Chem. Int. Ed. Engl.34, 1555±1573.
Figure 1
A view of the molecule of (I), with displacement ellipsoids drawn at the 50% probability level. The unlabeled atoms are related to the labeled atoms by a center of symmetry.
Figure 2
Blessing, R. H. (1995).Acta Cryst.A51, 33±38. Brock, C. P. (2002).Acta Cryst.B58, 1025±1031.
Brock, C. P. & Duncan, L. L. (1994).Chem. Mater.6, 1307±1312.
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990).Acta Cryst.B46, 256± 262.
KoritsaÂnszky, T. & Menczel, G (1982).Acta Cryst.B38, 1617±1619.
Le MagueÁRes, P., Lindemann, S. V. & Kochi, J. K. (2001).Organometallics,20, 115±125.
Shan, N. & Jones, W. (2001).Acta Cryst.E57, o1233±o1244.
Sheldrick, G. M. (1994). SHELXTL Version 5. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (1996).SADABS. University of GoÈttingen, Germany. Siemens (1995).SMARTandSAINT. Siemens Analytical X-ray Instruments
Inc., Madison, Wisconsin, USA.
Wieczorek, M. W., Bokiy, N. G. & Struchkov, Y. T. (1975).Roczn.Chem.49, 1737±1741; perStruct. Rep.41B, 135±136.
supporting information
sup-1 Acta Cryst. (2003). E59, o1089–o1091
supporting information
Acta Cryst. (2003). E59, o1089–o1091 [https://doi.org/10.1107/S1600536803014223]
Durenedimethanol
Doyle Britton
2,3,5,6-tetramethyl-1,4-phenylenedimethanol
Crystal data C12H18O2 Mr = 194.26
Tetragonal, I41/a
Hall symbol: -I 4ad a = 16.042 (4) Å c = 8.656 (2) Å V = 2227.6 (9) Å3 Z = 8
F(000) = 848
Dx = 1.159 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3471 reflections θ = 2.5–25.0°
µ = 0.08 mm−1 T = 174 K Prism, colorless 0.38 × 0.22 × 0.22 mm
Data collection
Siemens SMART area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
ω scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996; Blessing, 1995) Tmin = 0.97, Tmax = 0.98
5239 measured reflections 990 independent reflections 871 reflections with I > 2σ(I) Rint = 0.025
θmax = 25.1°, θmin = 2.5° h = −19→13
k = −18→19 l = −10→9
Refinement Refinement on F2
Least-squares matrix: full R[F2 > 2σ(F2)] = 0.043 wR(F2) = 0.104 S = 1.13 990 reflections 70 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 atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(F
o2) + (0.04P)2 + 1.83P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.16 e Å−3
Δρmin = −0.16 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
O1 0.24536 (7) 0.57226 (7) 1.01908 (13) 0.0349 (3)
C1 0.22445 (9) 0.69735 (9) 0.86954 (17) 0.0273 (4)
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sup-2 Acta Cryst. (2003). E59, o1089–o1091
C3 0.28809 (9) 0.75530 (9) 0.89553 (17) 0.0285 (4)
C4 0.19336 (10) 0.64436 (10) 1.00204 (18) 0.0346 (4)
H4A 0.1941 0.6773 1.0987 0.042*
H4B 0.1352 0.6268 0.9819 0.042*
C6 0.33110 (12) 0.76037 (12) 1.0506 (2) 0.0456 (5)
H6A 0.3130 0.8109 1.1046 0.055*
H6B 0.3916 0.7622 1.0353 0.055*
H6C 0.3166 0.7113 1.1125 0.055*
C5 0.12389 (13) 0.62375 (13) 0.6888 (3) 0.0555 (6)
H5A 0.1346 0.6004 0.5861 0.067*
H5B 0.0678 0.6480 0.6915 0.067*
H5C 0.1280 0.5795 0.7664 0.067*
H1 0.2254 (13) 0.5450 (13) 1.098 (3) 0.054 (6)*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
O1 0.0455 (7) 0.0308 (6) 0.0285 (6) 0.0067 (5) 0.0128 (5) 0.0084 (5)
C1 0.0304 (8) 0.0264 (7) 0.0250 (8) 0.0037 (6) 0.0072 (6) 0.0031 (6)
C2 0.0304 (8) 0.0291 (8) 0.0307 (8) −0.0028 (6) 0.0007 (6) 0.0011 (6)
C3 0.0336 (8) 0.0281 (8) 0.0239 (8) 0.0025 (6) −0.0012 (6) −0.0002 (6)
C4 0.0401 (9) 0.0335 (8) 0.0301 (8) 0.0069 (7) 0.0116 (7) 0.0074 (7)
C6 0.0595 (12) 0.0459 (10) 0.0315 (9) −0.0017 (9) −0.0116 (9) 0.0030 (8)
C5 0.0557 (12) 0.0538 (12) 0.0568 (13) −0.0225 (10) −0.0116 (10) 0.0107 (10)
Geometric parameters (Å, º)
O1—C4 1.434 (2) C4—H4A 0.9900
O1—H1 0.87 (2) C4—H4B 0.9900
C1—C3 1.399 (2) C6—H6A 0.9800
C1—C2 1.400 (2) C6—H6B 0.9800
C1—C4 1.512 (2) C6—H6C 0.9800
C2—C3i 1.401 (2) C5—H5A 0.9800
C2—C5 1.512 (2) C5—H5B 0.9800
C3—C2i 1.402 (2) C5—H5C 0.9800
C3—C6 1.512 (2)
C4—O1—H1 105.8 (13) C1—C4—H4B 109.7
C3—C1—C2 120.29 (13) H4A—C4—H4B 108.2
C3—C1—C4 119.48 (14) C3—C6—H6A 109.5
C2—C1—C4 120.18 (14) C3—C6—H6B 109.5
C1—C2—C3i 119.93 (14) H6A—C6—H6B 109.5
C1—C2—C5 121.24 (14) C3—C6—H6C 109.5
C3i—C2—C5 118.78 (15) H6A—C6—H6C 109.5
C1—C3—C2i 119.73 (14) H6B—C6—H6C 109.5
C1—C3—C6 120.78 (14) C2—C5—H5A 109.5
C2i—C3—C6 119.49 (14) C2—C5—H5B 109.5
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sup-3 Acta Cryst. (2003). E59, o1089–o1091
O1—C4—H4A 109.7 C2—C5—H5C 109.5
C1—C4—H4A 109.7 H5A—C5—H5C 109.5
O1—C4—H4B 109.7 H5B—C5—H5C 109.5
C3—C1—C2—C3i −2.7 (2) C2—C1—C3—C6 −177.21 (15)
C4—C1—C2—C3i 174.78 (14) C4—C1—C3—C6 5.3 (2)
C3—C1—C2—C5 174.74 (15) C3—C1—C4—O1 −84.95 (17)
C4—C1—C2—C5 −7.8 (2) C2—C1—C4—O1 97.56 (17)
C2—C1—C3—C2i 2.7 (2) C1—C2—C5—H5B 101.7
C4—C1—C3—C2i −174.80 (14) C1—C3—C6—H6A −107.3
