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

Oishi, T.; Yamamoto, H.; Sugai, T.; Fukaya, K.; Yamaguchi, Y.; Watanabe, A.; Sato, T.; Chida, N.

doi:10.1107/S2056989015016783

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ISSN: 2056-9890

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

doi:10.1107/S2056989015016783

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

Takeshi Oishi,^a ^* Hiroaki Yamamoto,^b Tomoya Sugai,^b Keisuke Fukaya,^b Yu Yamaguchi,^b Ami Watanabe,^b Takaaki Sato ^b and Noritaka Chida ^b

^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.

Keywords: crystal structure; hydrogen bonds; paclitaxel; cyclohexane; hydroxy groups.

CCDC reference: 1422946

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[11.3.1.0^3,10.0^4,7]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 ).

2. Structural commentary

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.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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
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) 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).

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
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 ), 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).

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). 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. C-bound H atoms were positioned geometrically with C—H = 0.98–1.00 Å, and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). The hydroxy H atoms were placed guided by difference maps, with O—H = 0.84 Å and with U_iso(H) = 1.5U_eq(O).

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₁₆O₄
M_r	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)
V (Å³)	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 )
T_min, T_max	0.97, 0.97
No. of measured, independent and observed [I > 2σ(I)] reflections	8165, 1612, 1205
R_int	0.037
(sin θ/λ)_max (Å⁻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
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.27
Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXS2013 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), Mercury (Macrae et al., 2006 ), publCIF (Westrip, 2010 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1422946

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2056989015016783/is5419sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015016783/is5419Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015016783/is5419Isup3.cml

checkCIF report

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[11.3.1.0^3,10.0^4,7]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, P2₁2₁2_1] 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

Refinement top

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

	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.
	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.]
	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.]
	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

C₉H₁₆O₄	D_x = 1.358 Mg m⁻³
M_r = 188.22	Melting point: 360.2 K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.7403 (5) Å	Cell parameters from 2733 reflections
b = 18.1498 (11) Å	θ = 2.7–24.7°
c = 6.7335 (5) Å	µ = 0.11 mm⁻¹
β = 103.281 (2)°	T = 90 K
V = 920.66 (11) Å³	Prism, colorless
Z = 4	0.28 × 0.27 × 0.25 mm
F(000) = 408

Data collection top

Bruker D8 Venture diffractometer	1612 independent reflections
Radiation source: fine-focus sealed tube	1205 reflections with I > 2σ(I)
Multilayered confocal mirror monochromator	R_int = 0.037
Detector resolution: 10.4167 pixels mm^-1	θ_max = 25.0°, θ_min = 2.7°
φ and ω scans	h = −9→8
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −21→21
T_min = 0.97, T_max = 0.97	l = −8→7
8165 measured reflections

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0407P)² + 0.4103P] where P = (F_o² + 2F_c²)/3
1612 reflections	(Δ/σ)_max = 0.008
121 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₉H₁₆O₄	V = 920.66 (11) Å³
M_r = 188.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7403 (5) Å	µ = 0.11 mm⁻¹
b = 18.1498 (11) Å	T = 90 K
c = 6.7335 (5) Å	0.28 × 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)
T_min = 0.97, T_max = 0.97	R_int = 0.037
8165 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.01	Δρ_max = 0.25 e Å⁻³
1612 reflections	Δρ_min = −0.27 e Å⁻³
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

	x	y	z	U_iso*/U_eq
O1	0.27151 (15)	0.55328 (6)	1.12431 (17)	0.0191 (3)
C2	0.4342 (2)	0.58896 (9)	1.2186 (3)	0.0209 (4)
H2A	0.5326	0.5725	1.158	0.025*
H2B	0.4662	0.5796	1.3675	0.025*
C3	0.3914 (2)	0.66886 (9)	1.1734 (3)	0.0204 (4)
H3A	0.327	0.6902	1.271	0.025*
H3B	0.5002	0.698	1.1772	0.025*
O4	0.28135 (15)	0.66576 (6)	0.97209 (18)	0.0177 (3)
C5	0.1875 (2)	0.59633 (9)	0.9519 (2)	0.0154 (4)
C6	−0.0045 (2)	0.60871 (9)	0.9585 (2)	0.0139 (4)
H6A	−0.0085	0.6365	1.0839	0.017*
H6B	−0.0617	0.5603	0.9663	0.017*
C7	−0.1103 (2)	0.65073 (8)	0.7741 (3)	0.0139 (4)
C8	−0.0926 (2)	0.61203 (9)	0.5774 (2)	0.0141 (4)
H8	−0.1427	0.5614	0.5804	0.017*
C9	0.1009 (2)	0.60306 (9)	0.5692 (3)	0.0161 (4)
H9A	0.1551	0.6523	0.5649	0.019*
H9B	0.1079	0.5764	0.443	0.019*
C10	0.2047 (2)	0.56059 (9)	0.7546 (3)	0.0160 (4)
H10A	0.1598	0.5094	0.7496	0.019*
H10B	0.3315	0.5586	0.7499	0.019*
C11	−0.3033 (2)	0.65735 (10)	0.7850 (3)	0.0209 (4)
H11A	−0.3108	0.6838	0.9097	0.031*
H11B	−0.3544	0.608	0.7868	0.031*
H11C	−0.3692	0.6845	0.6658	0.031*
O12	−0.04355 (15)	0.72524 (6)	0.77185 (18)	0.0170 (3)
H12	0.0652	0.726	0.828	0.026*
O13	−0.19319 (15)	0.64738 (6)	0.40008 (17)	0.0179 (3)
H13	−0.1446	0.6875	0.3825	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0174 (6)	0.0186 (7)	0.0174 (7)	−0.0029 (5)	−0.0040 (5)	0.0046 (5)
C2	0.0167 (9)	0.0220 (10)	0.0206 (10)	−0.0018 (8)	−0.0024 (7)	−0.0001 (8)
C3	0.0197 (10)	0.0203 (10)	0.0186 (10)	−0.0022 (8)	−0.0012 (8)	−0.0022 (8)
O4	0.0167 (6)	0.0158 (6)	0.0178 (7)	−0.0057 (5)	−0.0021 (5)	0.0019 (5)
C5	0.0157 (9)	0.0124 (8)	0.0162 (9)	−0.0029 (7)	−0.0001 (7)	0.0041 (7)
C6	0.0165 (9)	0.0130 (9)	0.0130 (9)	−0.0021 (7)	0.0048 (7)	−0.0011 (7)
C7	0.0154 (9)	0.0099 (8)	0.0166 (10)	−0.0008 (7)	0.0042 (7)	0.0003 (7)
C8	0.0160 (9)	0.0114 (9)	0.0132 (9)	−0.0010 (7)	−0.0002 (7)	0.0010 (7)
C9	0.0178 (9)	0.0162 (9)	0.0147 (9)	−0.0001 (7)	0.0045 (7)	−0.0020 (7)
C10	0.0135 (9)	0.0164 (9)	0.0188 (10)	0.0001 (7)	0.0051 (7)	−0.0005 (7)
C11	0.0181 (9)	0.0223 (10)	0.0233 (10)	0.0017 (8)	0.0071 (8)	0.0005 (8)
O12	0.0176 (6)	0.0129 (6)	0.0195 (7)	−0.0011 (5)	0.0021 (5)	−0.0007 (5)
O13	0.0192 (7)	0.0171 (6)	0.0145 (7)	−0.0021 (5)	−0.0019 (5)	0.0036 (5)

Geometric parameters (Å, º) top

O1—C5	1.4265 (19)	C7—C11	1.517 (2)
O1—C2	1.428 (2)	C7—C8	1.532 (2)
C2—C3	1.503 (2)	C8—O13	1.4200 (19)
C2—H2A	0.99	C8—C9	1.520 (2)
C2—H2B	0.99	C8—H8	1.0
C3—O4	1.427 (2)	C9—C10	1.529 (2)
C3—H3A	0.99	C9—H9A	0.99
C3—H3B	0.99	C9—H9B	0.99
O4—C5	1.4453 (19)	C10—H10A	0.99
C5—C10	1.512 (2)	C10—H10B	0.99
C5—C6	1.514 (2)	C11—H11A	0.98
C6—C7	1.526 (2)	C11—H11B	0.98
C6—H6A	0.99	C11—H11C	0.98
C6—H6B	0.99	O12—H12	0.84
C7—O12	1.4491 (19)	O13—H13	0.84

C5—O1—C2	107.70 (12)	O12—C7—C8	108.41 (13)
O1—C2—C3	102.52 (13)	C11—C7—C8	111.28 (14)
O1—C2—H2A	111.3	C6—C7—C8	109.66 (13)
C3—C2—H2A	111.3	O13—C8—C9	111.85 (13)
O1—C2—H2B	111.3	O13—C8—C7	112.27 (13)
C3—C2—H2B	111.3	C9—C8—C7	111.41 (13)
H2A—C2—H2B	109.2	O13—C8—H8	107.0
O4—C3—C2	102.13 (13)	C9—C8—H8	107.0
O4—C3—H3A	111.3	C7—C8—H8	107.0
C2—C3—H3A	111.3	C8—C9—C10	111.21 (14)
O4—C3—H3B	111.3	C8—C9—H9A	109.4
C2—C3—H3B	111.3	C10—C9—H9A	109.4
H3A—C3—H3B	109.2	C8—C9—H9B	109.4
C3—O4—C5	107.54 (12)	C10—C9—H9B	109.4
O1—C5—O4	105.99 (12)	H9A—C9—H9B	108.0
O1—C5—C10	111.37 (13)	C5—C10—C9	111.42 (13)
O4—C5—C10	108.24 (13)	C5—C10—H10A	109.3
O1—C5—C6	108.93 (13)	C9—C10—H10A	109.3
O4—C5—C6	110.10 (13)	C5—C10—H10B	109.3
C10—C5—C6	112.02 (13)	C9—C10—H10B	109.3
C5—C6—C7	113.40 (13)	H10A—C10—H10B	108.0
C5—C6—H6A	108.9	C7—C11—H11A	109.5
C7—C6—H6A	108.9	C7—C11—H11B	109.5
C5—C6—H6B	108.9	H11A—C11—H11B	109.5
C7—C6—H6B	108.9	C7—C11—H11C	109.5
H6A—C6—H6B	107.7	H11A—C11—H11C	109.5
O12—C7—C11	106.50 (13)	H11B—C11—H11C	109.5
O12—C7—C6	110.42 (13)	C7—O12—H12	109.5
C11—C7—C6	110.50 (14)	C8—O13—H13	109.5

C5—O1—C2—C3	30.97 (17)	C5—C6—C7—C8	53.80 (17)
O1—C2—C3—O4	−37.36 (16)	O12—C7—C8—O13	−61.28 (17)
C2—C3—O4—C5	30.55 (17)	C11—C7—C8—O13	55.53 (17)
C2—O1—C5—O4	−12.62 (16)	C6—C7—C8—O13	178.10 (12)
C2—O1—C5—C10	104.89 (15)	O12—C7—C8—C9	65.06 (16)
C2—O1—C5—C6	−131.06 (14)	C11—C7—C8—C9	−178.13 (13)
C3—O4—C5—O1	−12.23 (16)	C6—C7—C8—C9	−55.56 (17)
C3—O4—C5—C10	−131.81 (14)	O13—C8—C9—C10	−176.36 (12)
C3—O4—C5—C6	105.44 (15)	C7—C8—C9—C10	57.07 (18)
O1—C5—C6—C7	−176.78 (12)	O1—C5—C10—C9	174.98 (12)
O4—C5—C6—C7	67.39 (16)	O4—C5—C10—C9	−68.89 (16)
C10—C5—C6—C7	−53.12 (18)	C6—C5—C10—C9	52.69 (18)
C5—C6—C7—O12	−65.60 (17)	C8—C9—C10—C5	−55.09 (18)
C5—C6—C7—C11	176.83 (13)

Hydrogen-bond geometry (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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

Experimental details

Crystal data
Chemical formula	C₉H₁₆O₄
M_r	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)
V (Å³)	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 diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2014)
T_min, T_max	0.97, 0.97
No. of measured, independent and observed [I > 2σ(I)] reflections	8165, 1612, 1205
R_int	0.037
(sin θ/λ)_max (Å⁻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
Δρ_max, Δρ_min (e Å⁻³)	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

Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Volume 71| Part 10| October 2015| Pages 1181-1184

doi:10.1107/S2056989015016783

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

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

3. Supramolecular features