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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 10| October 2015| Pages 1181-1184

Crystal structure of (±)-(7RS,8SR)-7-methyl-1,4-dioxa­spiro­[4.5]decane-7,8-diol

CROSSMARK_Color_square_no_text.svg

aSchool of Medicine, Keio University, Hiyoshi 4-1-1, Kohoku-ku, Yokohama 223-8521, Japan, and bDepartment of Applied Chemistry, Faculty of Science and Technology, Keio University, Hiyoshi 3-14-1, Kohoku-ku, Yokohama 223-8522, Japan
*Correspondence e-mail: oec@keio.jp

Edited by H. Ishida, Okayama University, Japan (Received 3 September 2015; accepted 8 September 2015; online 17 September 2015)

In the title compound, C9H16O4, the five-membered dioxolane ring adopts a twist conformation; two adjacent C atoms deviate alternately from the mean plane of other atoms by −0.297 (4) and 0.288 (4) Å. The spiro-fused cyclo­hexane ring shows a chair form. The hy­droxy group substituted in an axial position makes an intra­molecular O—H⋯O hydrogen bond with one of the O atoms in the cyclic ether, forming an S(6) ring motif. In the crystal, the O—H⋯O hydrogen bond involving the equatorial hy­droxy group connects the mol­ecules into a zigzag chain with a C(5) motif running along the c axis.

1. Chemical context

Paclitaxel (systematic name: (1S,2S,3R,4S,7R,9S,10S,12R,15S)-4,12-diacet­oxy-1,9-dihy­droxy-15-{[(2R,3S)-3-benzoylamino-2-hy­droxy-3-phen­yl]propano­yl}­oxy-10,14,17,17-tetramethyl-11-oxo-6-oxa­tetra­cyclo­[11.3.1.03,10.04,7]hepta­dec-13-en-2-yl benzoate) is a well-known natural diterpenoid with a potent anti­tumor activity (Wall & Wani, 1995[Wall, M. E. & Wani, M. C. (1995). ACS Symp. Ser. 583, 18-30.]). Its rather complicated structure and significant bioactivity have attracted chemical and medicinal inter­ests. While we recently reported several structures of the compounds (Oishi, Yamaguchi et al., 2015[Oishi, T., Yamaguchi, Y., Fukaya, K., Sugai, T., Watanabe, A., Sato, T. & Chida, N. (2015). Acta Cryst. E71, 8-11.]; Oishi, Fukaya et al., 2015a[Oishi, T., Fukaya, K., Yamaguchi, Y., Sugai, T., Watanabe, A., Sato, T. & Chida, N. (2015a). Acta Cryst. E71, 466-472.],b[Oishi, T., Fukaya, K., Yamaguchi, Y., Sugai, T., Watanabe, A., Sato, T. & Chida, N. (2015b). Acta Cryst. E71, 490-493.]) obtained in the synthesis of paclitaxel (Fukaya, Tanaka et al., 2015[Fukaya, K., Tanaka, Y., Sato, A. C., Kodama, K., Yamazaki, H., Ishimoto, T., Nozaki, Y., Iwaki, Y. M., Yuki, Y., Umei, K., Sugai, T., Yamaguchi, Y., Watanabe, A., Oishi, T., Sato, T. & Chida, N. (2015). Org. Lett. 17, 2570-2573.]; Fukaya, Kodama et al., 2015[Fukaya, K., Kodama, K., Tanaka, Y., Yamazaki, H., Sugai, T., Yamaguchi, Y., Watanabe, A., Oishi, T., Sato, T. & Chida, N. (2015). Org. Lett. 17, 2574-2577.]), the title compound has been prepared in an efficient synthetic approach to furnish the highly functionalized cyclo­hexane unit (Fukaya, Sugai et al., 2015[Fukaya, K., Sugai, T., Sugai, T., Yamaguchi, Y., Watanabe, A., Yamamoto, H., Sato, T. & Chida, N. (2015). In preparation.]). Although the title compound has been reported first with a different synthetic procedure, any stereochemical or conformational assignment was not mentioned (Li et al., 1981[Li, Y.-L., Pan, X.-F., Huang, W.-K., Wang, Y.-K. & Li, Y.-C. (1981). Acta Chim. Sin. 39, 937-939.]).

[Scheme 1]

2. Structural commentary

The mol­ecular structure of the title compound is shown in Fig. 1[link]. The dioxolane ring (O1/C2/C3/O4/C5) adopts a twist form with puckering parameters of Q(2) = 0.3523 (16) Å and φ(2) = 233.8 (3)°. Atoms C2 and C3 deviate from the mean plane of the other three atoms by −0.297 (4) and 0.288 (4) Å, respectively. The cyclo­hexane ring (C5–C10) adopts a chair form with puckering parameters of Q = 0.5560 (18) Å, θ = 3.32 (18)°, φ = 193 (3)°, Q(2) = 0.0323 (17) Å and Q(3) = 0.5551 (18) Å. The C5—O1, C7—C11 and C8—O13 bonds of equatorially oriented substituents make angles of 68.30 (9), 69.85 (9) and 75.76 (9)°, respectively, with the normal to the Cremer and Pople plane of the cyclo­hexane ring. The axially oriented hy­droxy group forms an intra­molecular O—H⋯O hydrogen bond (O12—H12⋯O4; Table 1[link]), generating an S(6) graph-set motif. In this ring motif, five atoms (C5—O4⋯H12—O12—O7) are nearly coplanar with a maximum deviation of 0.012 (5) Å for atom O4.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O12—H12⋯O4 0.84 2.05 2.7838 (16) 146
O13—H13⋯O12i 0.84 1.99 2.8093 (16) 166
C6—H6B⋯O1ii 0.99 2.61 3.5631 (19) 162
Symmetry codes: (i) [x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]; (ii) -x, -y+1, -z+2.
[Figure 1]
Figure 1
The mol­ecular structure of the title compound, showing the atom labels. Displacement ellipsoids are drawn at the 50% probability level. The yellow dotted line indicates the intra­molecular O—H⋯O hydrogen bond. Only H atoms connected to O and chiral C atoms are shown for clarity.

3. Supra­molecular features

The crystal packing features an inter­molecular O—H⋯O hydrogen bond (O13—H13⋯O12i; Table 1[link]) connecting enanti­omers related by a glide plane to form a chain structure with a C(5) graph-set motif running along the c axis (Fig. 2[link]). An inter­molecular C—H⋯O inter­action (C6—H6B⋯O1ii; Table 1[link]) with a slightly longer distance, leading to form a sheet parallel to (100), is also observed (Fig. 3[link]).

[Figure 2]
Figure 2
A partial packing view showing the chain structure. Yellow lines indicate the intra­molecular O—H⋯O hydrogen bonds. Purple dashed lines indicate the inter­molecular O—H⋯O hydrogen bonds. Only H atoms involved in hydrogen bonds are shown for clarity. [Symmetry code: (i) x, −y + [{3\over 2}], z − [{1\over 2}].]
[Figure 3]
Figure 3
A packing diagram viewed down the c axis. Black dotted lines indicate the inter­molecular C—H⋯O inter­actions. Yellow lines and purple dashed lines indicate the intra- and inter­molecular O—H⋯O hydrogen bonds, respectively. Only H atoms involved in hydrogen bonds are shown for clarity. [Symmetry code: (ii) −x, −y + 1, −z + 2.]

4. Database survey

In the Cambridge Structural Database (CSD, Version 5.36, November 2014; Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]), 266 structures containing a 7-methyl-1,4-dioxa­spiro­[4.5]decane skeleton, (a), are registered (Fig. 4[link]). These include six compounds with 7,8-di­oxy-substituents. Two of them (JIQFIY and JIQGAR; Collins et al., 1998[Collins, D. J., Hibberd, A. I., Skelton, B. W. & White, A. H. (1998). Aust. J. Chem. 51, 681-694.]), synthesized from D-glucose, are closely related to the title compound [(b); racemic, P21/c], which are its 9,10-dimeth­oxy-8-O-methyl [(c); chiral, P212121] and 9,10-dimeth­oxy-6-phenyl-8-O-methyl [(d); chiral, P212121] derivatives. In the crystal structures of (c) and (d), the dioxolane rings adopt twist forms and the cyclo­hexane rings show chair forms. The intra­molecular O—H⋯O hydrogen bond is also observed in (c), but not in (d).

[Figure 4]
Figure 4
(a) 7-Methyl-1,4-dioxa­spiro­[4.5]decane; as the core structure for database survey, (b) the title compound, and its (c) 9,10-dimeth­oxy-8-O-methyl and (d) 9,10-dimeth­oxy-6-phenyl-8-O-methyl derivatives.

5. Synthesis and crystallization

The title compound was afforded in an improved synthetic approach of paclitaxel from 3-methyl­anisole (Fukaya, Sugai et al., 2015[Fukaya, K., Sugai, T., Sugai, T., Yamaguchi, Y., Watanabe, A., Yamamoto, H., Sato, T. & Chida, N. (2015). In preparation.]). Purification was carried out by silica gel column chromatography, and colorless crystals were obtained from an ethyl acetate solution by slow evaporation at ambient temperature. M.p. 359–360 K. HRMS (ESI) m/z calculated for C9H16O4Na+ [M + Na]+: 211.0946; found: 211.0936. Analysis calculated for C9H16O4: C 57.43, H 8.57%; found: C 57.51, H 8.50%. It is noted that the crystals grown from a diethyl ether solution under a pentane-saturated atmosphere were non-merohedral twins, and the structure is essentially the same as that reported here.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. C-bound H atoms were positioned geometrically with C—H = 0.98–1.00 Å, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The hy­droxy H atoms were placed guided by difference maps, with O—H = 0.84 Å and with Uiso(H) = 1.5Ueq(O).

Table 2
Experimental details

Crystal data
Chemical formula C9H16O4
Mr 188.22
Crystal system, space group Monoclinic, P21/c
Temperature (K) 90
a, b, c (Å) 7.7403 (5), 18.1498 (11), 6.7335 (5)
β (°) 103.281 (2)
V3) 920.66 (11)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.11
Crystal size (mm) 0.28 × 0.27 × 0.25
 
Data collection
Diffractometer Bruker D8 Venture
Absorption correction Multi-scan (SADABS; Bruker, 2014[Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.97, 0.97
No. of measured, independent and observed [I > 2σ(I)] reflections 8165, 1612, 1205
Rint 0.037
(sin θ/λ)max−1) 0.595
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.092, 1.01
No. of reflections 1612
No. of parameters 121
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.25, −0.27
Computer programs: APEX2 and SAINT (Bruker, 2014[Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS2013 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]), publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Chemical context top

\ Paclitaxel (systematic name: (1S,2S,3R,4S,7R,9S,10S,\ 12R,15S)-4,12-di­acet­oxy-1,9-di­hydroxy-15-{[(2R,\ 3S)-3-benzoyl­amino-2-hy­droxy-3-phenyl]­propanoyl}­oxy-10,14,17,17-\ tetra­methyl-11-oxo-6-oxa­tetra­cyclo­[11.3.1.03,10.04,7]heptadec-13-en-2-yl benzoate) is a well-known natural diterpenoid with a potent anti­tumor activity (Wall & Wani, 1995). Its rather complicated structure and significant bioactivity have attracted chemical and medicinal inter­ests. While we recently reported several structures of the compounds (Oishi, Yamaguchi et al., 2015; Oishi, Fukaya et al., 2015a,b) obtained in the synthesis of paclitaxel (Fukaya, Tanaka et al., 2015; Fukaya, Kodama et al., 2015), the title compound has been prepared in an efficient synthetic approach to furnish the highly functionalized cyclo­hexane unit (Fukaya, Sugai et al., 2015). Although the title compound has been reported first with a different synthetic procedure, any stereochemical or conformational assignment was not mentioned (Li et al., 1981).

Structural commentary top

The molecular structure of the title compound is shown in Fig. 1. The dioxolane ring (O1/C2/C3/O4/C5) adopts a twist form with puckering parameters of Q(2) = 0.3523 (16) Å and φ(2) = 233.8 (3)°. Atoms C2 and C3 deviate from the mean plane of the other three atoms by –0.297 (4) and 0.288 (4) Å, respectively. The cyclo­hexane ring (C5–C10) adopts a chair form with puckering parameters of Q = 0.5560 (18) Å, θ = 3.32 (18)°, φ = 193 (3)°, Q(2) = 0.0323 (17) Å and Q(3) = 0.5551 (18) Å. The C5—O1, C7—C11 and C8—O13 bonds of equatorially oriented substituents make angles of 68.30 (9), 69.85 (9) and 75.76 (9)°, respectively, with the normal to the Cremer and Pople plane of the cyclo­hexane ring. The axially oriented hy­droxy group forms an intra­molecular O—H···O hydrogen bond (O12—H12···O4; Table 1), generating an S(6) graph-set motif. In this ring motif, five atoms (C5—O4···H12—O12—O7) are nearly coplanar with a maximum deviation of 0.012 (5) Å for atom O4.

Supra­molecular features top

The crystal packing is stabilized by an inter­molecular O—H···O hydrogen bond (O13—H13···O12i; Table 1) connecting enanti­omers related by a glide plane to form a chain structure with a C(5) graph-set motif running along the c axis (Fig. 2). An inter­molecular C—H···O inter­action (C6—H6B···O1ii; Table 1) with a slightly longer distance, leading to form a sheet parallel to (100), is also observed (Fig. 3).

Database survey top

In the Cambridge Structural Database (CSD, Version 5.36, November 2014; Groom & Allen, 2014), 266 structures containing a 7-methyl-1,4-dioxa­spiro­[4.5]decane skeleton, (a), are registered (Fig. 4). These include six compounds with 7,8-di­oxy-substituents. Two of them (JIQFIY and JIQGAR; Collins et al., 1998), synthesized from D-glucose, are closely related to the title compound [(b); racemic, P21/c], which are its 9,10-di­meth­oxy-8-O-methyl [(c); chiral, P212121] and 9,10-di­meth­oxy-6-phenyl-8-O-methyl [(d); chiral, P212121] derivatives. In the crystal structures of (c) and (d), the dioxolane rings adopt twist forms and the cyclo­hexane rings show chair forms. The intra­molecular O—H···O hydrogen bond is also observed in (c), but not in (d).

Synthesis and crystallization top

The title compound was afforded in an improved synthetic approach of paclitaxel from 3-methyl­anisole (Fukaya, Sugai et al., 2015). Purification was carried out by silica gel column chromatography, and colorless crystals were obtained from an ethyl acetate solution by slow evaporation at ambient temperature. M.p. 359–360 K. HRMS (ESI) m/z calculated for C9H16O4Na+ [M + Na]+: 211.0946; found: 211.0936. Analysis calculated for C9H16O4: C 57.43, H 8.57%; found: C 57.51, H 8.50%. It is noted that the crystals grown from a di­ethyl ether solution under a pentane-saturated atmosphere were non-merohedral twins, and the structure is essentially the same as that reported here.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. C-bound H atoms were positioned geometrically with C—H = 0.98–1.00 Å, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The hy­droxy H atoms were placed guided by difference maps, with O—H = 0.84 Å and with Uiso(H) = 1.5Ueq(O).

Related literature top

For related literature, see: Collins et al. (1998); Fukaya, Kodama et al. (2015); Fukaya, Sugai et al. (2015); Fukaya, Tanaka et al. (2015); Groom & Allen (2014); Li et al. (1981); Oishi, Fukaya et al. (2015a, b); Oishi, Yamaguchi et al. (2015); Wall & Wani (1995).

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing the atom labels. Displacement ellipsoids are drawn at the 50% probability level. The yellow dotted line indicates the intramolecular O—H···O hydrogen bond. Only H atoms connected to O and chiral C atoms are shown for clarity.
[Figure 2] Fig. 2. A partial packing view showing the chain structure. Yellow lines indicate the intramolecular O—H···O hydrogen bonds. Purple dashed lines indicate the intermolecular O—H···O hydrogen bonds. Only H atoms involved in hydrogen bonds are shown for clarity. [Symmetry code: (i) x, -y + 3/2, z - 1/2.]
[Figure 3] Fig. 3. A packing diagram viewed down the c axis. Black dotted lines indicate the intermolecular C—H···O interactions. Yellow lines and purple dashed lines indicate the intra- and intermolecular O—H···O hydrogen bonds, respectively. Only H atoms involved in hydrogen bonds are shown for clarity. [Symmetry code: (ii) -x, -y + 1, -z + 2.]
[Figure 4] Fig. 4. (a) 7-Methyl-1,4-dioxaspiro[4.5]decane; as the core structure for database survey, (b) the title compound, and its (c) 9,10-dimethoxy-8-O-methyl and (d) 9,10-dimethoxy-6-phenyl-8-O-methyl derivatives.
(±)-(7RS,8SR)-7-Methyl-1,4-dioxaspiro[4.5]decane-7,8-diol top
Crystal data top
C9H16O4Dx = 1.358 Mg m3
Mr = 188.22Melting point: 360.2 K
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.7403 (5) ÅCell parameters from 2733 reflections
b = 18.1498 (11) Åθ = 2.7–24.7°
c = 6.7335 (5) ŵ = 0.11 mm1
β = 103.281 (2)°T = 90 K
V = 920.66 (11) Å3Prism, colorless
Z = 40.28 × 0.27 × 0.25 mm
F(000) = 408
Data collection top
Bruker D8 Venture
diffractometer
1612 independent reflections
Radiation source: fine-focus sealed tube1205 reflections with I > 2σ(I)
Multilayered confocal mirror monochromatorRint = 0.037
Detector resolution: 10.4167 pixels mm-1θmax = 25.0°, θmin = 2.7°
φ and ω scansh = 98
Absorption correction: multi-scan
(SADABS; Bruker, 2014)
k = 2121
Tmin = 0.97, Tmax = 0.97l = 87
8165 measured reflections
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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0407P)2 + 0.4103P]
where P = (Fo2 + 2Fc2)/3
1612 reflections(Δ/σ)max = 0.008
121 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
C9H16O4V = 920.66 (11) Å3
Mr = 188.22Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.7403 (5) ŵ = 0.11 mm1
b = 18.1498 (11) ÅT = 90 K
c = 6.7335 (5) Å0.28 × 0.27 × 0.25 mm
β = 103.281 (2)°
Data collection top
Bruker D8 Venture
diffractometer
1612 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2014)
1205 reflections with I > 2σ(I)
Tmin = 0.97, Tmax = 0.97Rint = 0.037
8165 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.092H-atom parameters constrained
S = 1.01Δρmax = 0.25 e Å3
1612 reflectionsΔρmin = 0.27 e Å3
121 parameters
Special details top

Experimental. IR (KBr) 3476, 3398, 2986, 2950, 2931, 2895, 1448, 1419, 1397, 1356, 1229, 1120, 1083, 1060, 1013, 952, 840, 696 cm-1; 1H NMR (500 MHz, CDCl3) δ (p.p.m.) 4.02–3.91 (m, 4H), 3.73 (s, 1H), 3.33 (ddd, J = 10.7, 10.6, 4.9 Hz, 1H), 2.03 (d, J = 10.6 Hz, 1H), 1.94–1.86 (m, 2H), 1.78–1.56 (m, 4H), 1.25 (d, J = 0.9 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ (p.p.m.) 108.7 (C), 74.0 (CH), 72.5 (C), 64.7 (CH2), 64.4 (CH2), 44.1 (CH2), 33.2 (CH2), 28.4 (CH2), 26.2 (CH3).

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.

Problematic one reflection with |I(obs)-I(calc)|/σW(I) greater than 10 (0 2 0) has been omitted in the final refinement.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.27151 (15)0.55328 (6)1.12431 (17)0.0191 (3)
C20.4342 (2)0.58896 (9)1.2186 (3)0.0209 (4)
H2A0.53260.57251.1580.025*
H2B0.46620.57961.36750.025*
C30.3914 (2)0.66886 (9)1.1734 (3)0.0204 (4)
H3A0.3270.69021.2710.025*
H3B0.50020.6981.17720.025*
O40.28135 (15)0.66576 (6)0.97209 (18)0.0177 (3)
C50.1875 (2)0.59633 (9)0.9519 (2)0.0154 (4)
C60.0045 (2)0.60871 (9)0.9585 (2)0.0139 (4)
H6A0.00850.63651.08390.017*
H6B0.06170.56030.96630.017*
C70.1103 (2)0.65073 (8)0.7741 (3)0.0139 (4)
C80.0926 (2)0.61203 (9)0.5774 (2)0.0141 (4)
H80.14270.56140.58040.017*
C90.1009 (2)0.60306 (9)0.5692 (3)0.0161 (4)
H9A0.15510.65230.56490.019*
H9B0.10790.57640.4430.019*
C100.2047 (2)0.56059 (9)0.7546 (3)0.0160 (4)
H10A0.15980.50940.74960.019*
H10B0.33150.55860.74990.019*
C110.3033 (2)0.65735 (10)0.7850 (3)0.0209 (4)
H11A0.31080.68380.90970.031*
H11B0.35440.6080.78680.031*
H11C0.36920.68450.66580.031*
O120.04355 (15)0.72524 (6)0.77185 (18)0.0170 (3)
H120.06520.7260.8280.026*
O130.19319 (15)0.64738 (6)0.40008 (17)0.0179 (3)
H130.14460.68750.38250.027*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0174 (6)0.0186 (7)0.0174 (7)0.0029 (5)0.0040 (5)0.0046 (5)
C20.0167 (9)0.0220 (10)0.0206 (10)0.0018 (8)0.0024 (7)0.0001 (8)
C30.0197 (10)0.0203 (10)0.0186 (10)0.0022 (8)0.0012 (8)0.0022 (8)
O40.0167 (6)0.0158 (6)0.0178 (7)0.0057 (5)0.0021 (5)0.0019 (5)
C50.0157 (9)0.0124 (8)0.0162 (9)0.0029 (7)0.0001 (7)0.0041 (7)
C60.0165 (9)0.0130 (9)0.0130 (9)0.0021 (7)0.0048 (7)0.0011 (7)
C70.0154 (9)0.0099 (8)0.0166 (10)0.0008 (7)0.0042 (7)0.0003 (7)
C80.0160 (9)0.0114 (9)0.0132 (9)0.0010 (7)0.0002 (7)0.0010 (7)
C90.0178 (9)0.0162 (9)0.0147 (9)0.0001 (7)0.0045 (7)0.0020 (7)
C100.0135 (9)0.0164 (9)0.0188 (10)0.0001 (7)0.0051 (7)0.0005 (7)
C110.0181 (9)0.0223 (10)0.0233 (10)0.0017 (8)0.0071 (8)0.0005 (8)
O120.0176 (6)0.0129 (6)0.0195 (7)0.0011 (5)0.0021 (5)0.0007 (5)
O130.0192 (7)0.0171 (6)0.0145 (7)0.0021 (5)0.0019 (5)0.0036 (5)
Geometric parameters (Å, º) top
O1—C51.4265 (19)C7—C111.517 (2)
O1—C21.428 (2)C7—C81.532 (2)
C2—C31.503 (2)C8—O131.4200 (19)
C2—H2A0.99C8—C91.520 (2)
C2—H2B0.99C8—H81.0
C3—O41.427 (2)C9—C101.529 (2)
C3—H3A0.99C9—H9A0.99
C3—H3B0.99C9—H9B0.99
O4—C51.4453 (19)C10—H10A0.99
C5—C101.512 (2)C10—H10B0.99
C5—C61.514 (2)C11—H11A0.98
C6—C71.526 (2)C11—H11B0.98
C6—H6A0.99C11—H11C0.98
C6—H6B0.99O12—H120.84
C7—O121.4491 (19)O13—H130.84
C5—O1—C2107.70 (12)O12—C7—C8108.41 (13)
O1—C2—C3102.52 (13)C11—C7—C8111.28 (14)
O1—C2—H2A111.3C6—C7—C8109.66 (13)
C3—C2—H2A111.3O13—C8—C9111.85 (13)
O1—C2—H2B111.3O13—C8—C7112.27 (13)
C3—C2—H2B111.3C9—C8—C7111.41 (13)
H2A—C2—H2B109.2O13—C8—H8107.0
O4—C3—C2102.13 (13)C9—C8—H8107.0
O4—C3—H3A111.3C7—C8—H8107.0
C2—C3—H3A111.3C8—C9—C10111.21 (14)
O4—C3—H3B111.3C8—C9—H9A109.4
C2—C3—H3B111.3C10—C9—H9A109.4
H3A—C3—H3B109.2C8—C9—H9B109.4
C3—O4—C5107.54 (12)C10—C9—H9B109.4
O1—C5—O4105.99 (12)H9A—C9—H9B108.0
O1—C5—C10111.37 (13)C5—C10—C9111.42 (13)
O4—C5—C10108.24 (13)C5—C10—H10A109.3
O1—C5—C6108.93 (13)C9—C10—H10A109.3
O4—C5—C6110.10 (13)C5—C10—H10B109.3
C10—C5—C6112.02 (13)C9—C10—H10B109.3
C5—C6—C7113.40 (13)H10A—C10—H10B108.0
C5—C6—H6A108.9C7—C11—H11A109.5
C7—C6—H6A108.9C7—C11—H11B109.5
C5—C6—H6B108.9H11A—C11—H11B109.5
C7—C6—H6B108.9C7—C11—H11C109.5
H6A—C6—H6B107.7H11A—C11—H11C109.5
O12—C7—C11106.50 (13)H11B—C11—H11C109.5
O12—C7—C6110.42 (13)C7—O12—H12109.5
C11—C7—C6110.50 (14)C8—O13—H13109.5
C5—O1—C2—C330.97 (17)C5—C6—C7—C853.80 (17)
O1—C2—C3—O437.36 (16)O12—C7—C8—O1361.28 (17)
C2—C3—O4—C530.55 (17)C11—C7—C8—O1355.53 (17)
C2—O1—C5—O412.62 (16)C6—C7—C8—O13178.10 (12)
C2—O1—C5—C10104.89 (15)O12—C7—C8—C965.06 (16)
C2—O1—C5—C6131.06 (14)C11—C7—C8—C9178.13 (13)
C3—O4—C5—O112.23 (16)C6—C7—C8—C955.56 (17)
C3—O4—C5—C10131.81 (14)O13—C8—C9—C10176.36 (12)
C3—O4—C5—C6105.44 (15)C7—C8—C9—C1057.07 (18)
O1—C5—C6—C7176.78 (12)O1—C5—C10—C9174.98 (12)
O4—C5—C6—C767.39 (16)O4—C5—C10—C968.89 (16)
C10—C5—C6—C753.12 (18)C6—C5—C10—C952.69 (18)
C5—C6—C7—O1265.60 (17)C8—C9—C10—C555.09 (18)
C5—C6—C7—C11176.83 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12—H12···O40.842.052.7838 (16)146
O13—H13···O12i0.841.992.8093 (16)166
C6—H6B···O1ii0.992.613.5631 (19)162
Symmetry codes: (i) x, y+3/2, z1/2; (ii) x, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12—H12···O40.842.052.7838 (16)146
O13—H13···O12i0.841.992.8093 (16)166
C6—H6B···O1ii0.992.613.5631 (19)162
Symmetry codes: (i) x, y+3/2, z1/2; (ii) x, y+1, z+2.

Experimental details

Crystal data
Chemical formulaC9H16O4
Mr188.22
Crystal system, space groupMonoclinic, P21/c
Temperature (K)90
a, b, c (Å)7.7403 (5), 18.1498 (11), 6.7335 (5)
β (°) 103.281 (2)
V3)920.66 (11)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.28 × 0.27 × 0.25
Data collection
DiffractometerBruker D8 Venture
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2014)
Tmin, Tmax0.97, 0.97
No. of measured, independent and
observed [I > 2σ(I)] reflections
8165, 1612, 1205
Rint0.037
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.092, 1.01
No. of reflections1612
No. of parameters121
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.27

Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXS2013 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), Mercury (Macrae et al., 2006), publCIF (Westrip, 2010) and PLATON (Spek, 2009).

 

Acknowledgements

This research was partially supported by the Keio Gijuku Fukuzawa Memorial Fund for the Advancement of Education and Research. We also thank Professor S. Ohba (Keio University, Japan) for his valuable advice.

References

First citationBruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCollins, D. J., Hibberd, A. I., Skelton, B. W. & White, A. H. (1998). Aust. J. Chem. 51, 681–694.  CSD CrossRef CAS Google Scholar
First citationFukaya, K., Kodama, K., Tanaka, Y., Yamazaki, H., Sugai, T., Yamaguchi, Y., Watanabe, A., Oishi, T., Sato, T. & Chida, N. (2015). Org. Lett. 17, 2574–2577.  CrossRef CAS PubMed Google Scholar
First citationFukaya, K., Sugai, T., Sugai, T., Yamaguchi, Y., Watanabe, A., Yamamoto, H., Sato, T. & Chida, N. (2015). In preparation.  Google Scholar
First citationFukaya, K., Tanaka, Y., Sato, A. C., Kodama, K., Yamazaki, H., Ishimoto, T., Nozaki, Y., Iwaki, Y. M., Yuki, Y., Umei, K., Sugai, T., Yamaguchi, Y., Watanabe, A., Oishi, T., Sato, T. & Chida, N. (2015). Org. Lett. 17, 2570–2573.  CrossRef CAS PubMed Google Scholar
First citationGroom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671.  Web of Science CSD CrossRef CAS Google Scholar
First citationLi, Y.-L., Pan, X.-F., Huang, W.-K., Wang, Y.-K. & Li, Y.-C. (1981). Acta Chim. Sin. 39, 937–939.  CAS Google Scholar
First citationMacrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationOishi, T., Fukaya, K., Yamaguchi, Y., Sugai, T., Watanabe, A., Sato, T. & Chida, N. (2015a). Acta Cryst. E71, 466–472.  CSD CrossRef IUCr Journals Google Scholar
First citationOishi, T., Fukaya, K., Yamaguchi, Y., Sugai, T., Watanabe, A., Sato, T. & Chida, N. (2015b). Acta Cryst. E71, 490–493.  CSD CrossRef IUCr Journals Google Scholar
First citationOishi, T., Yamaguchi, Y., Fukaya, K., Sugai, T., Watanabe, A., Sato, T. & Chida, N. (2015). Acta Cryst. E71, 8–11.  CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWall, M. E. & Wani, M. C. (1995). ACS Symp. Ser. 583, 18–30.  CrossRef CAS Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 71| Part 10| October 2015| Pages 1181-1184
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