organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890
Volume 69| Part 8| August 2013| Pages o1303-o1304

4-(2-Hy­dr­oxy­eth­­oxy)phenol

aInstitute of Organic Chemistry, Karlsruhe Institute of Technology, Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany, bLaboratory of Inorganic Chemistry, Department of Chemistry, University of Helsinki, PO Box 55, 00014 University of Helsinki, Finland, and cInstitute of Organic Chemistry, Institute of Toxicology and Genetics, Karlsruhe Institute of Technology, Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany
*Correspondence e-mail: braese@kit.edu

(Received 27 June 2013; accepted 17 July 2013; online 24 July 2013)

The asymmetric unit of the title compound, C8H10O3, contains four mol­ecules, which differ in the orientation of the hy­­droxy­ethyl group [O—C—C—O torsion angles = −168.89 (17), 72.9 (2), −65.8 (2) and 71.8 (2)°], as well as the orientation of the hy­droxy H atoms. Furthermore, the crystal structure displays two different types of strong hydrogen bond. The first is between an alcohol O—H and another alcohol O atom, and the second between an alcohol O—H group and an ether O atom. Additional weak hydrogen bonds between C—H groups and ether O atoms stabilize the structure.

Related literature

For the synthesis of the title compound, see: Read & Miller (1932[Read, R. R. & Miller, E. (1932). J. Am. Chem. Soc. 54, 1195-1199.]). For its biological activity, see: Smit et al. (1992[Smit, N. P. M., Peters, K., Menko, W., Westerhof, W., Pavel, S. & Riley, P. A. (1992). Melanoma Res. 2, 295-304.]). For its use in the synthesis of biologically active materials, see: Ding et al. (2009[Ding, Q., Jiang, N., Yang, S., Zhang, J. & Zhang, Z. (2009). US Patent Appl. Publ. US 20090156610 A1 20090618.]); Pitterna et al. (2004[Pitterna, T., Böger, M. & Maienfisch, P. (2004). Chimia, 58, 108-116.]); Petrović & Brückner (2011[Petrović, D. & Brückner, R. (2011). Org. Lett. 13, 6524-6527.]). For its application in polymer synthesis, see: Nakano et al. (2000[Nakano, S., Nakanishi, S., Izumi, K., Yoshioka, M. & Mochizuki, O. (2000). Japanese Patent Kokai Tokkyo Koho JP2000327924A20001128.]); Kaneda et al. (2004[Kaneda, K., Kuriya, Y. & Nashiko, T. (2004). Japanese Patent Kokai Tokkyo Koho JP2004175943A20040624.]); Xi et al. (2010[Xi, H., Ju, S., Chen, Z. & Sun, X. (2010). Chem. Lett. 39, 415-417.]). For its use as a substrate for dye synthesis, see: Kelly (1996[Kelly, S. (1996). European Patent Appl. EP748852A219961218.]). For information about the cuprate, used for synthesis, see: Normant et al. (1980[Normant, J. F., Alexakis, A. & Cahiez, G. (1980). Tetrahedron Lett. 21, 935-938.]). For its reactivity, see: Semmelhack et al. (1985[Semmelhack, M. F., Keller, L., Sato, T., Spiess, E. J. & Wulff, W. (1985). J. Org. Chem. 50, 5566-5574.]).

[Scheme 1]

Experimental

Crystal data
  • C8H10O3

  • Mr = 154.16

  • Triclinic, [P \overline 1]

  • a = 10.0388 (10) Å

  • b = 10.2425 (8) Å

  • c = 15.0692 (11) Å

  • α = 83.916 (8)°

  • β = 86.470 (9)°

  • γ = 77.124 (8)°

  • V = 1500.8 (2) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 123 K

  • 0.16 × 0.08 × 0.04 mm

Data collection
  • Bruker Nonius KappaCCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.]) Tmin = 0.910, Tmax = 0.997

  • 17940 measured reflections

  • 5282 independent reflections

  • 3204 reflections with I > 2σ(I)

  • Rint = 0.058

Refinement
  • R[F2 > 2σ(F2)] = 0.051

  • wR(F2) = 0.110

  • S = 1.02

  • 5282 reflections

  • 421 parameters

  • 48 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.21 e Å−3

  • Δρmin = −0.27 e Å−3

Table 1
Selected torsion angles (°)

O1A—C2A—C3A—O4A −168.89 (17)
O1B—C2B—C3B—O4B 72.9 (2)
O1C—C2C—C3C—O4C −65.8 (2)
O1D—C2D—C3D—O4D 71.8 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1A—H1A⋯O1Ci 0.84 (1) 1.85 (1) 2.671 (2) 165 (2)
O8A—H8A⋯O1Bii 0.84 (1) 1.74 (1) 2.565 (2) 170 (2)
O1B—H1B⋯O1Diii 0.84 (1) 1.88 (1) 2.707 (2) 168 (2)
O8B—H8B⋯O1Ai 0.84 (1) 1.79 (1) 2.617 (2) 169 (2)
O1C—H1C⋯O4D 0.84 (1) 2.12 (1) 2.830 (2) 142 (2)
O8C—H8C⋯O8Biv 0.84 (1) 1.88 (1) 2.721 (2) 176 (2)
O1D—H1D⋯O8Ciii 0.84 (1) 2.02 (1) 2.800 (2) 155 (2)
O8D—H8D⋯O8Av 0.84 (1) 1.88 (1) 2.707 (2) 167 (2)
C2A—H2A1⋯O4B 0.99 2.48 3.452 (3) 168
C2B—H2B2⋯O4A 0.99 2.58 3.450 (3) 147
C2C—H2C1⋯O8Avi 0.99 2.44 3.402 (3) 163
C9B—H9B⋯O4Avii 0.95 2.54 3.361 (3) 145
C2C—H2C2⋯O8Dviii 0.99 2.49 3.337 (3) 144
C2D—H2D2⋯O4C 0.99 2.57 3.478 (3) 152
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y, -z+2; (iii) -x+1, -y, -z+1; (iv) x-1, y, z; (v) x+2, y, z-1; (vi) x+1, y, z-1; (vii) x+1, y, z; (viii) -x+2, -y+1, -z.

Data collection: COLLECT (Nonius, 1999[Nonius (1999). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: EVALCCD (Duisenberg et al., 2003[Duisenberg, A. J. M., Kroon-Batenburg, L. M. J. & Schreurs, A. M. M. (2003). J. Appl. Cryst. 36, 220-229.]); data reduction: EVALCCD; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

Although the synthesis of the title compound, Scheme 1, has been known for about 80 years (Read & Miller, 1932), its crystal structure has never been reported. It has been used in syntheses of biologically active materials such as anti-cancer agents (Ding et al., 2009) as it is toxic to melanoma cells (Smit et al., 1992). It has also been used for the synthesis of an acaricide and insecticide substance (Pitterna et al., 2004) and for the synthesis of steroid precursors (Petrović & Brückner, 2011). Further uses are as a monomer in polymer synthesis including liquid crystalline polymers (Nakano et al., 2000) and coating rubbers (Kaneda et al., 2004), in the synthesis of a surface active piperazine derivative (Xi et al., 2010) and as a starting material for the synthesis of liquid-crystalline dyes (Kelly, 1996). We intended to do a 1,4 addition of a Normant cuprate (Normant et al., 1980) to 1,4-dioxaspiro[4.5]deca-6,9-dien-8-one, but under the conditions applied we observed the title compound as the only product. A similar observation has been made (Semmelhack et al., 1985) in the reaction of the same quinone with nBuLi. The intended synthesis along with the actual reaction is shown in Fig. 1. Fig. 2 shows the asymmetric unit with four independent molecules. They mainly differ in the orientation of the hydroxyethyl chain as well as in the orientation of the alcohol H atoms. The least-squares fit (Fig. 3) shows that molecules B and D are very similar and only differ in the orientation of the alcohol-H. Molecule C is similar to B, but the orientation of O1 differs. Molecule A shows a very different orientation of O1 (see also Table 1). Fig. 4 illustrates the packing including all hydrogen bonds. There is no obvious pattern, but there are different types of hydrogen bond resulting in different orientations of the H atoms. The strong hydrogen bonds O—H···O can be divided into those where the second oxygen is part of another alcohol function and those where the second oxygen is part of an ether function. Furthermore, there are also weak C—H···O hydrogen bonds.

Related literature top

For the synthesis of the title compound, see: Read & Miller (1932). For its biological activity, see: Smit et al. (1992). For its use in the synthesis of biologically active materials, see: Ding et al. (2009); Pitterna et al. (2004); Petrović & Brückner (2011). For its application in polymer synthesis, see: Nakano et al. (2000); Kaneda et al. (2004); Xi et al. (2010). For its use as a substrate for dye synthesis, see: Kelly (1996). For information about its use for [What type of?] synthesis, see: Normant et al. (1980). For its reactivity, see: Semmelhack et al. (1985).

Experimental top

The title compound was synthesized unplanned by the following procedure. A solution of 678 mg CuBr*SMe2 (3.30 mmol, 1.10 eq.) in 7 ml of dimethyl sulfide and 15 ml of ABS.THF was added at -30°C to a solution of 2.20 ml of methyl magnesium chloride (3 M in THF, 494 mg, 6.60 ml, 2.20 eq.) and the mixture was stirred at this temperature for 1 h. Then the mixture was cooled to -50°C and a solution of 460 mg 1,4-dioxaspiro[4.5]deca-6,9-dien-8-one (3.00 mmol, 1.00 eq.) in 5 ml of ABS.THF was added slowly to this mixture. Stirring was continued at this temperature for 15 h, then 11 ml of saturated ammonium chloride solution were added and the mixture was warmed to room temperature. Then air was bubbled through the solution for 1 h, the phases were separated and the aqueous phase was extracted with ethyl acetate (4 × 10 ml). The combined organic layers were dried over sodium sulfate and the solvent was removed under reduced pressure. The residue was purified by column chromatography (cyclohexane/ethyl acetate = 5:1) to yield the product as colorless crystals (361 mg, 2.34 mmol, 78%). The product crystallized from ethyl acetate after column chromatography by evaporation of the solvent with a rotavapor. m.p. = 90°C. The intended synthesis and the obtained product are shown in Fig. 1.

Refinement top

All H atoms were located in a difference electron density map. H atoms bound to carbon were refined using a riding model with aromatic C—H = 0.95 Å, secondary C—H = 0.99 Å, and with Uiso(H) = 1.2Ueq(C). The coordinates of the hydroxyl H atoms were refined freely with O—H distance retraints (0.84 (1) Å) and Uiso(H) = 1.5Ueq(O). Additionally 1,2 and 1,3 distance restraints (SADI) were used for the refinement of the hydroxyl group (for O—H and C—H(O) distance).

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: EVALCCD (Duisenberg et al., 2003); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Unexpected synthesis of title compound. Reagents and conditions: a) CuBr*SMe2, MeMgCl, SMe2, THF, -20°C to -50°C, 15 h, 78%.
[Figure 2] Fig. 2. Content of the asymmetric unit showing all four crystallographic independent molecules (displacement parameters are drawn at 50% probability level).
[Figure 3] Fig. 3. Least-squares fit of the four crystallographic independent molecules (fitted atoms O4, O8 and the C atoms of the phenyl ring).
[Figure 4] Fig. 4. Packing diagram showing the strong and weak hydrogen bonds.
4-(2-Hydroxyethoxy)phenol top
Crystal data top
C8H10O3Z = 8
Mr = 154.16F(000) = 656
Triclinic, P1Dx = 1.365 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.0388 (10) ÅCell parameters from 109 reflections
b = 10.2425 (8) Åθ = 1–25°
c = 15.0692 (11) ŵ = 0.10 mm1
α = 83.916 (8)°T = 123 K
β = 86.470 (9)°Plate, colourless
γ = 77.124 (8)°0.16 × 0.08 × 0.04 mm
V = 1500.8 (2) Å3
Data collection top
Bruker Nonius KappaCCD
diffractometer
5282 independent reflections
Radiation source: fine-focus sealed tube3204 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.058
rotation in ϕ and ω, 2° scansθmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 1111
Tmin = 0.910, Tmax = 0.997k = 1212
17940 measured reflectionsl = 1717
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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0433P)2 + 0.2157P]
where P = (Fo2 + 2Fc2)/3
5282 reflections(Δ/σ)max < 0.001
421 parametersΔρmax = 0.21 e Å3
48 restraintsΔρmin = 0.27 e Å3
Crystal data top
C8H10O3γ = 77.124 (8)°
Mr = 154.16V = 1500.8 (2) Å3
Triclinic, P1Z = 8
a = 10.0388 (10) ÅMo Kα radiation
b = 10.2425 (8) ŵ = 0.10 mm1
c = 15.0692 (11) ÅT = 123 K
α = 83.916 (8)°0.16 × 0.08 × 0.04 mm
β = 86.470 (9)°
Data collection top
Bruker Nonius KappaCCD
diffractometer
5282 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
3204 reflections with I > 2σ(I)
Tmin = 0.910, Tmax = 0.997Rint = 0.058
17940 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05148 restraints
wR(F2) = 0.110H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.21 e Å3
5282 reflectionsΔρmin = 0.27 e Å3
421 parameters
Special details top

Experimental. NMR spectra were recorded on a Bruker AM 400 spectrometer as solutions. Chemical shifts are expressed in parts per million (p.p.m., δ) downfield from tetramethylsilane (TMS) and are referenced to residual solvent peaks. The descriptions of signals include: m = multiplet, mc = centered multiplet, bs = broad singlet. The spectra were analyzed as first order patterns. The signal structure in the 13C NMR was analyzed by DEPT and is described as follows: + = primary or tertiary C-atom (positive DEPT signal), – = secondary C-atom (negative DEPT signal) and Cq = quaternary C-atom (no DEPT signal). MS(EI) (electron impact mass spectrometry) was performed by using a FINNIGAN MAT 90 (70 eV). The mass peak [M]+ and characteristic fragment peaks are given as mass to charge ratio (m/z) and the intensity of the signals were indicated in percent, relative to the intensity of the base signal (100%). IR (infrared spectroscopy) was recorded on a FT–IR Bruker alpha and intensities of the signals are characterized as follows: vs (very strong, 0–10% transmission), s (strong, 11–30% transmission), m (medium, 31–70% transmission), w (weak, 71–90% transmission) and vw (very weak, 91–100% transmission). Solvents, reagents and chemicals were purchased from Aldrich, Acros and Merck. All solvents, reagents and chemicals were used as purchased. Rf (cyclohexane/ethyl acetate = 1:1) = 0.30. – 1H NMR (400 MHz, acetone-D6): δ/p.p.m. = 3.80–3.84 (m, 2H, 2 × CH2), 3.92–3.97 (m, 3H, OH, 2 × CH2), 6.76 (mc, 4H, 4 × CHAr), 7.89 (bs, 1H, OHAr). – 13C NMR (100 MHz, acetone-D6): δ /p.p.m. = 61.51 (–, CH2), 71.09 (–, CH2), 116.36 (+, 2 × CHAr), 116.59 (+, 2 × CHAr), 152.21 (Cq, CAr), 153.30 (Cq, CAr). – IR (ATR) ν/cm-1 = 3468 (vw), 3250 (w), 2927 (w), 1862 (vw), 1604 (vw), 1505 (m), 1448 (m), 1367 (w), 1298 (w), 1274 (vw), 1215 (m), 1173 (w), 1073 (w), 1051 (m), 900 (w), 884 (w), 824 (m), 766 (w), 750 (m), 708 (w), 660 (w), 638 (w), 565 (w), 525 (w). – MS (70 eV, EI): m/z (%) = 154 (42) [M]+, 126 (55) [M – C2H4]+, 110 (100) [M – C2H4O]+, 98 (29) [M – C3H4O]+, 43 (24) [C2H3O]+. – HR-EIMS (C8H10O3): calc. 154.0630; found 154.0631.

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
O1A0.18232 (16)0.52473 (17)0.64327 (11)0.0282 (4)
H1A0.216 (2)0.551 (2)0.6858 (11)0.042*
C2A0.1518 (2)0.3973 (2)0.67249 (16)0.0259 (6)
H2A10.23460.33540.69680.031*
H2A20.12420.35810.62110.031*
C3A0.0380 (2)0.4116 (2)0.74358 (16)0.0203 (6)
H3A10.05680.46530.79040.024*
H3A20.05030.45690.71720.024*
O4A0.03354 (14)0.27818 (15)0.78052 (10)0.0209 (4)
C5A0.0668 (2)0.2645 (2)0.84542 (15)0.0163 (5)
C6A0.1655 (2)0.3708 (2)0.87354 (15)0.0193 (6)
H6A0.16610.46020.84880.023*
C7A0.2637 (2)0.3459 (2)0.93823 (16)0.0208 (6)
H7A0.33160.41860.95780.025*
C8A0.2632 (2)0.2165 (2)0.97428 (16)0.0207 (6)
O8A0.36470 (16)0.19848 (17)1.03765 (12)0.0330 (5)
H8A0.338 (2)0.1330 (19)1.0753 (13)0.050*
C9A0.1640 (2)0.1099 (2)0.94606 (16)0.0207 (6)
H9A0.16360.02060.97090.025*
C10A0.0659 (2)0.1338 (2)0.88185 (15)0.0188 (6)
H10A0.00220.06090.86260.023*
O1B0.31123 (17)0.00352 (17)0.83922 (11)0.0301 (4)
H1B0.279 (2)0.009 (2)0.7885 (9)0.045*
C2B0.3478 (2)0.1151 (2)0.86098 (16)0.0226 (6)
H2B10.35570.11020.92650.027*
H2B20.27400.19370.84340.027*
C3B0.4795 (2)0.1358 (2)0.81603 (15)0.0214 (6)
H3B10.51180.20620.84350.026*
H3B20.55020.05130.82300.026*
O4B0.45661 (14)0.17600 (15)0.72330 (10)0.0218 (4)
C5B0.5635 (2)0.2121 (2)0.67196 (15)0.0177 (5)
C6B0.5347 (2)0.2712 (2)0.58594 (15)0.0191 (6)
H6B0.44490.28400.56510.023*
C7B0.6359 (2)0.3114 (2)0.53055 (16)0.0199 (6)
H7B0.61560.35200.47190.024*
C8B0.7674 (2)0.2924 (2)0.56081 (15)0.0175 (5)
O8B0.87364 (15)0.33208 (16)0.50961 (11)0.0225 (4)
H8B0.8447 (19)0.377 (2)0.4622 (10)0.034*
C9B0.7968 (2)0.2323 (2)0.64565 (16)0.0207 (6)
H9B0.88700.21890.66600.025*
C10B0.6956 (2)0.1913 (2)0.70164 (15)0.0191 (6)
H10B0.71660.14930.75990.023*
O1C0.73642 (15)0.41867 (16)0.20251 (11)0.0263 (4)
H1C0.7721 (19)0.3400 (12)0.1917 (16)0.040*
C2C0.5993 (2)0.4495 (3)0.17389 (16)0.0269 (6)
H2C10.58920.38430.13210.032*
H2C20.58000.54040.14120.032*
C3C0.4975 (2)0.4452 (2)0.25053 (16)0.0228 (6)
H3C10.51110.50470.29530.027*
H3C20.40330.47650.22910.027*
O4C0.51734 (14)0.30920 (15)0.28973 (10)0.0213 (4)
C5C0.4156 (2)0.2782 (2)0.34923 (15)0.0177 (5)
C6C0.3025 (2)0.3728 (2)0.37613 (15)0.0186 (6)
H6C0.29350.46530.35600.022*
C7C0.2028 (2)0.3308 (2)0.43256 (15)0.0188 (6)
H7C0.12460.39500.45050.023*
C8C0.2159 (2)0.1967 (2)0.46305 (15)0.0182 (6)
O8C0.11772 (15)0.15193 (16)0.51912 (11)0.0246 (4)
H8C0.0441 (13)0.2101 (17)0.5174 (15)0.037*
C9C0.3306 (2)0.1033 (2)0.43747 (15)0.0202 (6)
H9C0.34050.01120.45900.024*
C10C0.4306 (2)0.1434 (2)0.38082 (15)0.0199 (6)
H10C0.50920.07920.36360.024*
O1D0.80068 (17)0.00017 (16)0.32015 (11)0.0271 (4)
H1D0.826 (2)0.0651 (14)0.3584 (12)0.041*
C2D0.8360 (2)0.1160 (2)0.34876 (16)0.0207 (6)
H2D10.84260.10460.41450.025*
H2D20.76260.19590.33330.025*
C3D0.9696 (2)0.1395 (2)0.30650 (15)0.0207 (6)
H3D11.00070.20750.33730.025*
H3D21.04030.05480.31210.025*
O4D0.95064 (14)0.18600 (15)0.21384 (10)0.0201 (4)
C5D1.0629 (2)0.2190 (2)0.16558 (15)0.0175 (5)
C6D1.0385 (2)0.2832 (2)0.08097 (15)0.0209 (6)
H6D0.94840.30290.05960.025*
C7D1.1431 (2)0.3191 (2)0.02700 (16)0.0223 (6)
H7D1.12510.36310.03110.027*
C8D1.2757 (2)0.2905 (2)0.05823 (15)0.0176 (5)
O8D1.37587 (15)0.32883 (16)0.00195 (11)0.0257 (4)
H8D1.4524 (11)0.288 (2)0.0213 (14)0.039*
C9D1.2997 (2)0.2284 (2)0.14293 (15)0.0191 (6)
H9D1.38960.20980.16460.023*
C10D1.1939 (2)0.1924 (2)0.19739 (16)0.0206 (6)
H10D1.21140.14990.25600.025*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0300 (10)0.0323 (10)0.0228 (11)0.0131 (8)0.0012 (8)0.0089 (8)
C2A0.0302 (14)0.0234 (14)0.0219 (15)0.0051 (11)0.0016 (11)0.0046 (11)
C3A0.0208 (13)0.0185 (13)0.0206 (14)0.0037 (10)0.0015 (10)0.0024 (11)
O4A0.0198 (9)0.0179 (9)0.0233 (10)0.0031 (7)0.0032 (7)0.0018 (7)
C5A0.0132 (12)0.0233 (14)0.0131 (14)0.0055 (10)0.0020 (10)0.0005 (11)
C6A0.0186 (12)0.0178 (13)0.0212 (15)0.0036 (10)0.0059 (11)0.0022 (11)
C7A0.0155 (12)0.0214 (13)0.0235 (15)0.0000 (10)0.0027 (11)0.0006 (11)
C8A0.0148 (12)0.0262 (14)0.0196 (14)0.0042 (11)0.0008 (10)0.0041 (11)
O8A0.0236 (9)0.0325 (11)0.0343 (12)0.0017 (8)0.0085 (8)0.0140 (8)
C9A0.0217 (13)0.0180 (13)0.0223 (15)0.0060 (11)0.0043 (11)0.0036 (11)
C10A0.0164 (12)0.0175 (13)0.0211 (15)0.0003 (10)0.0029 (10)0.0018 (11)
O1B0.0397 (10)0.0335 (10)0.0218 (11)0.0192 (8)0.0083 (8)0.0046 (8)
C2B0.0277 (14)0.0236 (14)0.0178 (14)0.0088 (11)0.0004 (11)0.0008 (11)
C3B0.0244 (13)0.0253 (14)0.0130 (14)0.0039 (11)0.0005 (10)0.0015 (11)
O4B0.0172 (8)0.0294 (9)0.0177 (10)0.0054 (7)0.0008 (7)0.0025 (8)
C5B0.0191 (12)0.0172 (12)0.0171 (14)0.0043 (10)0.0032 (10)0.0048 (10)
C6B0.0160 (12)0.0190 (13)0.0214 (15)0.0007 (10)0.0036 (11)0.0025 (11)
C7B0.0215 (13)0.0210 (13)0.0159 (14)0.0025 (11)0.0021 (11)0.0007 (11)
C8B0.0169 (12)0.0164 (12)0.0201 (15)0.0056 (10)0.0019 (11)0.0037 (10)
O8B0.0196 (9)0.0256 (10)0.0202 (10)0.0041 (7)0.0007 (7)0.0066 (8)
C9B0.0159 (12)0.0194 (13)0.0257 (16)0.0004 (10)0.0036 (11)0.0026 (11)
C10B0.0221 (13)0.0210 (13)0.0132 (14)0.0044 (11)0.0021 (10)0.0021 (10)
O1C0.0190 (9)0.0250 (10)0.0335 (11)0.0036 (8)0.0029 (7)0.0008 (8)
C2C0.0246 (14)0.0344 (15)0.0221 (15)0.0097 (12)0.0024 (11)0.0032 (12)
C3C0.0200 (13)0.0184 (13)0.0279 (15)0.0028 (11)0.0039 (11)0.0068 (11)
O4C0.0173 (8)0.0208 (9)0.0245 (10)0.0045 (7)0.0030 (7)0.0017 (7)
C5C0.0174 (12)0.0211 (13)0.0158 (14)0.0058 (10)0.0043 (10)0.0015 (10)
C6C0.0210 (13)0.0160 (13)0.0187 (14)0.0038 (10)0.0019 (11)0.0004 (10)
C7C0.0160 (12)0.0210 (13)0.0179 (14)0.0002 (10)0.0010 (10)0.0036 (11)
C8C0.0174 (12)0.0225 (13)0.0153 (14)0.0064 (11)0.0020 (10)0.0010 (11)
O8C0.0187 (9)0.0259 (10)0.0253 (10)0.0011 (7)0.0024 (8)0.0058 (8)
C9C0.0212 (13)0.0164 (13)0.0218 (15)0.0026 (10)0.0045 (11)0.0025 (11)
C10C0.0168 (12)0.0200 (13)0.0214 (15)0.0002 (10)0.0033 (10)0.0029 (11)
O1D0.0384 (10)0.0211 (9)0.0242 (11)0.0129 (8)0.0085 (8)0.0046 (8)
C2D0.0239 (13)0.0176 (13)0.0206 (14)0.0040 (10)0.0029 (11)0.0012 (11)
C3D0.0206 (13)0.0225 (13)0.0186 (15)0.0040 (11)0.0031 (10)0.0002 (11)
O4D0.0160 (8)0.0276 (9)0.0160 (10)0.0046 (7)0.0014 (7)0.0013 (7)
C5D0.0186 (12)0.0168 (12)0.0183 (14)0.0051 (10)0.0008 (10)0.0037 (11)
C6D0.0141 (12)0.0253 (14)0.0218 (15)0.0008 (11)0.0031 (11)0.0021 (11)
C7D0.0247 (13)0.0247 (14)0.0164 (14)0.0038 (11)0.0025 (11)0.0012 (11)
C8D0.0175 (12)0.0164 (12)0.0177 (14)0.0021 (10)0.0036 (10)0.0021 (10)
O8D0.0192 (9)0.0295 (10)0.0271 (11)0.0056 (8)0.0005 (8)0.0027 (8)
C9D0.0145 (12)0.0203 (13)0.0222 (15)0.0023 (10)0.0017 (10)0.0037 (11)
C10D0.0198 (13)0.0226 (13)0.0193 (15)0.0037 (11)0.0042 (11)0.0014 (11)
Geometric parameters (Å, º) top
O1A—C2A1.425 (3)O1C—C2C1.425 (3)
O1A—H1A0.840 (9)O1C—H1C0.835 (9)
C2A—C3A1.511 (3)C2C—C3C1.498 (3)
C2A—H2A10.9900C2C—H2C10.9900
C2A—H2A20.9900C2C—H2C20.9900
C3A—O4A1.429 (3)C3C—O4C1.431 (3)
C3A—H3A10.9900C3C—H3C10.9900
C3A—H3A20.9900C3C—H3C20.9900
O4A—C5A1.379 (3)O4C—C5C1.385 (3)
C5A—C6A1.383 (3)C5C—C6C1.389 (3)
C5A—C10A1.391 (3)C5C—C10C1.390 (3)
C6A—C7A1.388 (3)C6C—C7C1.385 (3)
C6A—H6A0.9500C6C—H6C0.9500
C7A—C8A1.377 (3)C7C—C8C1.382 (3)
C7A—H7A0.9500C7C—H7C0.9500
C8A—O8A1.382 (3)C8C—O8C1.382 (3)
C8A—C9A1.388 (3)C8C—C9C1.387 (3)
O8A—H8A0.838 (9)O8C—H8C0.840 (9)
C9A—C10A1.381 (3)C9C—C10C1.382 (3)
C9A—H9A0.9500C9C—H9C0.9500
C10A—H10A0.9500C10C—H10C0.9500
O1B—C2B1.420 (3)O1D—C2D1.426 (3)
O1B—H1B0.836 (9)O1D—H1D0.840 (9)
C2B—C3B1.495 (3)C2D—C3D1.506 (3)
C2B—H2B10.9900C2D—H2D10.9900
C2B—H2B20.9900C2D—H2D20.9900
C3B—O4B1.432 (3)C3D—O4D1.437 (3)
C3B—H3B10.9900C3D—H3D10.9900
C3B—H3B20.9900C3D—H3D20.9900
O4B—C5B1.379 (3)O4D—C5D1.389 (3)
C5B—C10B1.390 (3)C5D—C6D1.381 (3)
C5B—C6B1.390 (3)C5D—C10D1.387 (3)
C6B—C7B1.381 (3)C6D—C7D1.379 (3)
C6B—H6B0.9500C6D—H6D0.9500
C7B—C8B1.389 (3)C7D—C8D1.398 (3)
C7B—H7B0.9500C7D—H7D0.9500
C8B—C9B1.378 (3)C8D—O8D1.373 (3)
C8B—O8B1.387 (3)C8D—C9D1.374 (3)
O8B—H8B0.839 (8)O8D—H8D0.841 (9)
C9B—C10B1.389 (3)C9D—C10D1.393 (3)
C9B—H9B0.9500C9D—H9D0.9500
C10B—H10B0.9500C10D—H10D0.9500
C2A—O1A—H1A108.1 (14)C2C—O1C—H1C108.1 (14)
O1A—C2A—C3A110.68 (19)O1C—C2C—C3C112.20 (19)
O1A—C2A—H2A1109.5O1C—C2C—H2C1109.2
C3A—C2A—H2A1109.5C3C—C2C—H2C1109.2
O1A—C2A—H2A2109.5O1C—C2C—H2C2109.2
C3A—C2A—H2A2109.5C3C—C2C—H2C2109.2
H2A1—C2A—H2A2108.1H2C1—C2C—H2C2107.9
O4A—C3A—C2A106.28 (18)O4C—C3C—C2C107.90 (19)
O4A—C3A—H3A1110.5O4C—C3C—H3C1110.1
C2A—C3A—H3A1110.5C2C—C3C—H3C1110.1
O4A—C3A—H3A2110.5O4C—C3C—H3C2110.1
C2A—C3A—H3A2110.5C2C—C3C—H3C2110.1
H3A1—C3A—H3A2108.7H3C1—C3C—H3C2108.4
C5A—O4A—C3A117.24 (17)C5C—O4C—C3C116.79 (17)
O4A—C5A—C6A124.0 (2)O4C—C5C—C6C123.7 (2)
O4A—C5A—C10A115.83 (19)O4C—C5C—C10C116.1 (2)
C6A—C5A—C10A120.2 (2)C6C—C5C—C10C120.3 (2)
C5A—C6A—C7A119.5 (2)C7C—C6C—C5C119.3 (2)
C5A—C6A—H6A120.3C7C—C6C—H6C120.3
C7A—C6A—H6A120.3C5C—C6C—H6C120.3
C8A—C7A—C6A120.5 (2)C8C—C7C—C6C120.7 (2)
C8A—C7A—H7A119.8C8C—C7C—H7C119.7
C6A—C7A—H7A119.8C6C—C7C—H7C119.7
C7A—C8A—O8A117.6 (2)C7C—C8C—O8C121.9 (2)
C7A—C8A—C9A120.0 (2)C7C—C8C—C9C119.6 (2)
O8A—C8A—C9A122.4 (2)O8C—C8C—C9C118.4 (2)
C8A—O8A—H8A111.9 (15)C8C—O8C—H8C109.9 (13)
C10A—C9A—C8A119.9 (2)C10C—C9C—C8C120.4 (2)
C10A—C9A—H9A120.0C10C—C9C—H9C119.8
C8A—C9A—H9A120.0C8C—C9C—H9C119.8
C9A—C10A—C5A120.0 (2)C9C—C10C—C5C119.7 (2)
C9A—C10A—H10A120.0C9C—C10C—H10C120.2
C5A—C10A—H10A120.0C5C—C10C—H10C120.2
C2B—O1B—H1B110.2 (14)C2D—O1D—H1D108.4 (14)
O1B—C2B—C3B112.92 (19)O1D—C2D—C3D112.26 (19)
O1B—C2B—H2B1109.0O1D—C2D—H2D1109.2
C3B—C2B—H2B1109.0C3D—C2D—H2D1109.2
O1B—C2B—H2B2109.0O1D—C2D—H2D2109.2
C3B—C2B—H2B2109.0C3D—C2D—H2D2109.2
H2B1—C2B—H2B2107.8H2D1—C2D—H2D2107.9
O4B—C3B—C2B108.39 (18)O4D—C3D—C2D109.02 (18)
O4B—C3B—H3B1110.0O4D—C3D—H3D1109.9
C2B—C3B—H3B1110.0C2D—C3D—H3D1109.9
O4B—C3B—H3B2110.0O4D—C3D—H3D2109.9
C2B—C3B—H3B2110.0C2D—C3D—H3D2109.9
H3B1—C3B—H3B2108.4H3D1—C3D—H3D2108.3
C5B—O4B—C3B117.01 (17)C5D—O4D—C3D116.55 (16)
O4B—C5B—C10B123.5 (2)C6D—C5D—C10D119.6 (2)
O4B—C5B—C6B116.82 (19)C6D—C5D—O4D116.18 (19)
C10B—C5B—C6B119.6 (2)C10D—C5D—O4D124.3 (2)
C7B—C6B—C5B120.4 (2)C7D—C6D—C5D120.9 (2)
C7B—C6B—H6B119.8C7D—C6D—H6D119.5
C5B—C6B—H6B119.8C5D—C6D—H6D119.5
C6B—C7B—C8B119.9 (2)C6D—C7D—C8D119.7 (2)
C6B—C7B—H7B120.1C6D—C7D—H7D120.2
C8B—C7B—H7B120.1C8D—C7D—H7D120.2
C9B—C8B—O8B116.93 (19)O8D—C8D—C9D123.2 (2)
C9B—C8B—C7B119.9 (2)O8D—C8D—C7D117.3 (2)
O8B—C8B—C7B123.1 (2)C9D—C8D—C7D119.4 (2)
C8B—O8B—H8B110.6 (13)C8D—O8D—H8D108.3 (13)
C8B—C9B—C10B120.5 (2)C8D—C9D—C10D120.8 (2)
C8B—C9B—H9B119.7C8D—C9D—H9D119.6
C10B—C9B—H9B119.7C10D—C9D—H9D119.6
C9B—C10B—C5B119.6 (2)C5D—C10D—C9D119.6 (2)
C9B—C10B—H10B120.2C5D—C10D—H10D120.2
C5B—C10B—H10B120.2C9D—C10D—H10D120.2
O1A—C2A—C3A—O4A168.89 (17)O1C—C2C—C3C—O4C65.8 (2)
C2A—C3A—O4A—C5A177.71 (18)C2C—C3C—O4C—C5C166.76 (18)
C3A—O4A—C5A—C6A2.9 (3)C3C—O4C—C5C—C6C4.2 (3)
C3A—O4A—C5A—C10A178.20 (19)C3C—O4C—C5C—C10C174.66 (19)
O4A—C5A—C6A—C7A178.77 (19)O4C—C5C—C6C—C7C176.9 (2)
C10A—C5A—C6A—C7A0.1 (3)C10C—C5C—C6C—C7C1.9 (3)
C5A—C6A—C7A—C8A0.0 (3)C5C—C6C—C7C—C8C0.8 (3)
C6A—C7A—C8A—O8A179.3 (2)C6C—C7C—C8C—O8C179.7 (2)
C6A—C7A—C8A—C9A0.1 (3)C6C—C7C—C8C—C9C0.6 (3)
C7A—C8A—C9A—C10A0.0 (3)C7C—C8C—C9C—C10C0.9 (3)
O8A—C8A—C9A—C10A179.3 (2)O8C—C8C—C9C—C10C179.4 (2)
C8A—C9A—C10A—C5A0.1 (3)C8C—C9C—C10C—C5C0.2 (3)
O4A—C5A—C10A—C9A178.77 (19)O4C—C5C—C10C—C9C177.3 (2)
C6A—C5A—C10A—C9A0.2 (3)C6C—C5C—C10C—C9C1.6 (3)
O1B—C2B—C3B—O4B72.9 (2)O1D—C2D—C3D—O4D71.8 (2)
C2B—C3B—O4B—C5B174.15 (18)C2D—C3D—O4D—C5D176.98 (18)
C3B—O4B—C5B—C10B10.5 (3)C3D—O4D—C5D—C6D170.15 (19)
C3B—O4B—C5B—C6B170.01 (19)C3D—O4D—C5D—C10D9.3 (3)
O4B—C5B—C6B—C7B179.37 (19)C10D—C5D—C6D—C7D1.2 (3)
C10B—C5B—C6B—C7B1.1 (3)O4D—C5D—C6D—C7D179.3 (2)
C5B—C6B—C7B—C8B0.2 (3)C5D—C6D—C7D—C8D0.1 (3)
C6B—C7B—C8B—C9B0.6 (3)C6D—C7D—C8D—O8D179.8 (2)
C6B—C7B—C8B—O8B178.9 (2)C6D—C7D—C8D—C9D0.8 (3)
O8B—C8B—C9B—C10B179.1 (2)O8D—C8D—C9D—C10D179.6 (2)
C7B—C8B—C9B—C10B0.4 (3)C7D—C8D—C9D—C10D0.7 (3)
C8B—C9B—C10B—C5B0.5 (3)C6D—C5D—C10D—C9D1.3 (3)
O4B—C5B—C10B—C9B179.2 (2)O4D—C5D—C10D—C9D179.2 (2)
C6B—C5B—C10B—C9B1.3 (3)C8D—C9D—C10D—C5D0.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···O1Ci0.84 (1)1.85 (1)2.671 (2)165 (2)
O8A—H8A···O1Bii0.84 (1)1.74 (1)2.565 (2)170 (2)
O1B—H1B···O1Diii0.84 (1)1.88 (1)2.707 (2)168 (2)
O8B—H8B···O1Ai0.84 (1)1.79 (1)2.617 (2)169 (2)
O1C—H1C···O4D0.84 (1)2.12 (1)2.830 (2)142 (2)
O8C—H8C···O8Biv0.84 (1)1.88 (1)2.721 (2)176 (2)
O1D—H1D···O8Ciii0.84 (1)2.02 (1)2.800 (2)155 (2)
O8D—H8D···O8Av0.84 (1)1.88 (1)2.707 (2)167 (2)
C2A—H2A1···O4B0.992.483.452 (3)168
C2B—H2B2···O4A0.992.583.450 (3)147
C2C—H2C1···O8Avi0.992.443.402 (3)163
C9B—H9B···O4Avii0.952.543.361 (3)145
C2C—H2C2···O8Dviii0.992.493.337 (3)144
C2D—H2D2···O4C0.992.573.478 (3)152
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y, z+2; (iii) x+1, y, z+1; (iv) x1, y, z; (v) x+2, y, z1; (vi) x+1, y, z1; (vii) x+1, y, z; (viii) x+2, y+1, z.
Selected torsion angles (º) top
O1A—C2A—C3A—O4A168.89 (17)O1C—C2C—C3C—O4C65.8 (2)
O1B—C2B—C3B—O4B72.9 (2)O1D—C2D—C3D—O4D71.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···O1Ci0.840 (9)1.851 (11)2.671 (2)165 (2)
O8A—H8A···O1Bii0.838 (9)1.735 (9)2.565 (2)170 (2)
O1B—H1B···O1Diii0.836 (9)1.884 (9)2.707 (2)168 (2)
O8B—H8B···O1Ai0.839 (8)1.789 (9)2.617 (2)169 (2)
O1C—H1C···O4D0.835 (9)2.124 (13)2.830 (2)142.1 (18)
O8C—H8C···O8Biv0.840 (9)1.882 (9)2.721 (2)176 (2)
O1D—H1D···O8Ciii0.840 (9)2.018 (13)2.800 (2)155 (2)
O8D—H8D···O8Av0.841 (9)1.879 (9)2.707 (2)167 (2)
C2A—H2A1···O4B0.992.483.452 (3)168
C2B—H2B2···O4A0.992.583.450 (3)147
C2C—H2C1···O8Avi0.992.443.402 (3)163
C9B—H9B···O4Avii0.952.543.361 (3)145
C2C—H2C2···O8Dviii0.992.493.337 (3)144
C2D—H2D2···O4C0.992.573.478 (3)152
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y, z+2; (iii) x+1, y, z+1; (iv) x1, y, z; (v) x+2, y, z1; (vi) x+1, y, z1; (vii) x+1, y, z; (viii) x+2, y+1, z.
 

Acknowledgements

The authors acknowledge the Fonds der Chemischen Industrie and the Deutsche Forschungsgemeinschaft (DFG) (grant No. BR 1750-12-1) for financial support.

References

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Volume 69| Part 8| August 2013| Pages o1303-o1304
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