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(2S,3S)-2,6-Di­methyl­heptane-1,3-diol, C9H20O2, (I), was syn­thesized from the ketone (R)-4-benzyl-3-[(2R,3S)-3-hy­droxy-2,6-di­methyl­heptanoyl]-1,3-oxazolidin-2-one, C19H27NO4, (II), containing C atoms of known chirality. In both structures, strong hydrogen bonds between the hy­droxy groups form tape motifs. The contribution from weaker C—H...O hydrogen bonds is much more evident in the structure of (II), which furthermore contains an example of a direct short Osp3...Csp2 contact that represents a usually unrecognized type of inter­molecular inter­action.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113011852/gz3232sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113011852/gz3232Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113011852/gz3232IIsup3.hkl
Contains datablock II

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113011852/gz3232Isup4.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113011852/gz3232IIsup5.cml
Supplementary material

CCDC references: 950444; 950445

Comment top

The two isoforms of the nuclear oxysterol receptor liver X (LXRα and LXRβ) are relatively new drug targets within the nuclear receptor (NR) family. They are key players for increased cellular lipid accumulation and insulin resistance in skeletal muscle (Steffensen & Gustafsson, 2006; Laffitte et al., 2003). LXR agonists have been developed as desirable potential drugs for the treatment of cardiovascular diseases and metabolic syndrome, the regulation of inflammatory responses and immunity, and the treatment of skin diseases, and are effective for the treatment of murine models of atherosclerosis, diabetes and Alzheimer's disease (Viennois et al., 2011, 2012; Jakobsson et al., 2012). They also display anti-inflammatory activities (Zhu & Bakovic, 2008; Zhu et al., 2012; Solan et al., 2011) and act as agonists to inhibit cell proliferation in a number of major cancer forms (Viennois et al., 2012; Jakobsson et al., 2012). For instance, it has been shown that LXR agonists have anti-proliferative effects on LNCaP human prostate cancer cells, and activation of LXR also inhibits the proliferation of other prostate and breast cancer cell lines (Fukuchi et al., 2004). The ligand-binding pocket (LBP) of LXR allows binding of side-chain oxygenated sterols (OHCs). Recently, OHCs with a specific stereochemistry at the 23-hydroxylated side-chain C atom were also shown to regulate the hedgehog signalling pathway (Hh), a key developmental pathway playing multiple roles in embryonic development, including stem cell differentiation (Corman et al., 2012). This urged us to initiate a drug-design programme, starting with a retrosynthetic analysis for the establishment of synthetic routes to the pharmacophores in the different OHCs reported to affect the various diseases referred to above. Our first focus aimed at a stereoselective synthesis of the oxygenated side chains in 22(R)- and 22(S)-hydroxycholesterol, which have agonistic and antagonistic effects on LXR, respectively (Hessvik et al., 2012; Kase et al., 2012). (2S,3S)-2,6-Dimethylheptane-1,3-diol, (I), is a new chemical entity representing the oxygenated side chain in 22(S)-hydroxycholesterol, and is the starting material in a synthetic programme aimed at a new class of potential drug candidates as selective regulators of LXR receptor and the Hh pathway. This diol was obtained from the chiral ketone (R)-4-benzyl-3-[(2R,3S)-3-hydroxy-2,6-dimethylheptanoyl]-1,3-oxazolidin-2-one, (II), a compound with one asymmetric C atom with known absolute stereochemistry, which was made from commercially available starting materials.

The common fragment of (I) and (II) is easily recognized (Fig. 1) but their conformations are different at the C3—C4 bond, as the C2—C3—C4—C5 torsion angle is 173.22 (19)° for (I) (Table 1) but 55.4 (2)° for (II) (Table 2). The conformation of the bicyclic fragment of (II), characterized by a trans orientation [N1—C11—C13—C14 = 169.41 (17)°], is found for 53% of the molecules in the Cambridge Structural Database (CSD, Version 5.33 of November 2011; Allen, 2002) containing this group (157 occurrences in 141 entries). The trans configuration for the C11—N1—C1—C2 part is typical. Two structural analogues of (II), with a methoxy group attached to atom C4, have been described (Horneff et al., 2006) and they have different stereochemistries at atoms C2 and C3 [(2S,3S) and (2R,3R)], as well as different conformations for the aliphatic chain.

In the crystal structure of (I), individual diol molecules related by a twofold screw operation are connected by hydrogen bonds into tapes running along the a axis (Fig. 2a). A detailed illustration of a tape is provided in Fig. 3, revealing a ladder-like structure based on second-level R33(10) ring motifs (Bernstein et al., 1995). Hydrogen-bonding data are given in Table 3.

The structure of (II) has higher density (1.143 Mg m-3) than (I)?, but displays easily observable voids in the structure (Fig. 2b). Two voids within the unit cell together account for approximately 3.6% of the unit-cell volume. The void volume is approximately 17 Å3, which in theory is enough to accommodate a single water molecule, but there is no electron density indicating the presence of such. There is only one strong hydrogen-bond donor in the molecule, which participates in the generation of chains of molecules related by twofold screw symmetry parallel to the b axis. The simple chain is possibly strengthened by C8—H83···O1(-x + 2, y - 1/2, -z + 1) interactions (Fig. 4a and Table 4). The terminal isopentyl and phenyl groups of (II) are not involved in short contacts, but the five-membered oxazolidine rings stack parallel to the hydrogen-bonded chain and create not only a weaker C12—H122···O4(-x + 1,y - 1/2, -z + 1) hydrogen bond, but also a direct contact between atoms C10 and O3 [C···O = 2.993 (3) Å]. According to the classification scheme developed by Bertolasi et al. (2011, 2012), this represents a π* n electron donor–acceptor interaction. Using C—O—C and C—(CO)—C as search fragments, we found 230 such contacts shorter than 3.2 Å in the CSD, usually associated with O-atom electron donors in cyclic systems. In a simple molecule like tetrahydrofuran-3,4-dione, with a pair of carbonyl groups (Muller & Jacobson, 1980), this type of interaction is very marked (Fig. 4b).

Related literature top

For related literature, see: Allen (2002); Bernstein et al. (1995); Bertolasi et al. (2011, 2012); Corman et al. (2012); Fukuchi et al. (2004); Hessvik et al. (2012); Horneff et al. (2006); Jakobsson et al. (2012); Kase et al. (2012); Laffitte et al. (2003); Muller & Jacobson (1980); Solan et al. (2011); Steffensen & Gustafsson (2006); Viennois et al. (2011, 2012); Zhu & Bakovic (2008); Zhu et al. (2012).

Experimental top

Crystals were obtained as long needles for both compounds. For (II), they were very difficult to handle because they are easily bent and split along the longest dimension. No attempt was made to cut the specimen used for data collection. By mounting the crystals along the ϕ spindle axis, an approximately constant crystal volume was exposed to X-ray radiation upon ϕ and ω rotation during data collection, thus minimizing absorption effects.

Refinement top

The coordinates were refined for the hydroxy H atom. Other H atoms were positioned with idealized geometry and fixed C—H distances for CH3, CH2, CH (methine) and CH (sp2) groups of 0.98, 0.99, 1.00 and 0.95 Å, respectively, and with Uiso(H) = 1.5Ueq(C,O) for hydroxy and methyl groups or 1.2Ueq(C) otherwise. In the absence of significant anomalous scattering effects, 1020 and 1631 Friedel pairs were merged for (I) and (II), respectively.

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structures of (a) (I) and (b) (II), with the atom-numbering schemes. Displacement ellipsoids are drawn at the 50% probability level. Atoms C1–C9, which are common to both molecules, are shown in a darker grey tone.
[Figure 2] Fig. 2. The crystal packing of (a) (I) and (b) (II). Hydrogen bonds are shown as dashed lines. H atoms not involved in strong hydrogen bonds have been omitted for clarity and the colour coding is as in Fig. 1. Voids in (b) were calculated using Mercury (Macrae et al., 2008), with a 1.2 Å probe radius and 0.5 Å grid spacing. There are no voids in the structure of (I).
[Figure 3] Fig. 3. The hydrogen-bonding pattern in the structure of (I). Hydrogen bonds are shown as dashed lines. H atoms bonded to C atoms have been omitted for clarity. The two first-level C(6) chains (grey), and the conspicuous second-level C22(4) chain (blue in the electronic version of the paper) and R33(10) ring (red) motifs, have been highlighted. Generic atom labels have been used.
[Figure 4] Fig. 4. (a) The intermolecular interactions (dashed lines) in the structure of (II). For clarity, the benzyl and isopentyl groups are shown as spheres. The dominating zigzag C(6) chain (highlighted in grey) is corroborated by weaker C8—H83···O1(-x + 2, y - 1/2, -z + 1) hydrogen bonds. The second C—H···O interaction in the structure, C12—H121···O4(-x + 1, y - 1/2, -z + 1), connects the five-membered ring systems, together with a more unusual C10···O3(-x + 1, y + 1/2, -z + 1) contact of 2.993 (3) Å. (b) π* n electron donor–acceptor interactions (dashed lines) in the stucture of tetrahydrofuran-3,4-dione (Muller & Jacobson, 1980); both distances are 2.844 (3) Å.
(I) (2S,3S)-2,6-Dimethylheptane-1,3-diol top
Crystal data top
C9H20O2F(000) = 360
Mr = 160.25Dx = 1.045 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 4198 reflections
a = 5.964 (2) Åθ = 2.3–28.4°
b = 9.777 (4) ŵ = 0.07 mm1
c = 17.469 (6) ÅT = 105 K
V = 1018.6 (6) Å3Needle, colourless
Z = 41.85 × 0.14 × 0.13 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1487 independent reflections
Radiation source: fine-focus sealed tube1387 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
Detector resolution: 8.3 pixels mm-1θmax = 28.5°, θmin = 2.3°
Sets of exposures each taken over 0.5° ω rotation scansh = 77
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
k = 1212
Tmin = 0.851, Tmax = 0.990l = 2323
9215 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)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0462P)2 + 0.0839P]
where P = (Fo2 + 2Fc2)/3
1487 reflections(Δ/σ)max < 0.001
109 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = 0.14 e Å3
Crystal data top
C9H20O2V = 1018.6 (6) Å3
Mr = 160.25Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.964 (2) ŵ = 0.07 mm1
b = 9.777 (4) ÅT = 105 K
c = 17.469 (6) Å1.85 × 0.14 × 0.13 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1487 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
1387 reflections with I > 2σ(I)
Tmin = 0.851, Tmax = 0.990Rint = 0.026
9215 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.074H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.23 e Å3
1487 reflectionsΔρmin = 0.14 e Å3
109 parameters
Special details top

Experimental. Crystal mounted along the ϕ spindle axis

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
O10.94157 (16)0.67184 (9)0.03862 (5)0.0216 (2)
H11.073 (3)0.6534 (17)0.0531 (9)0.032*
O20.37216 (14)0.62368 (9)0.06085 (5)0.0220 (2)
H20.424 (3)0.6844 (17)0.0331 (9)0.033*
C10.8331 (2)0.54804 (12)0.01621 (6)0.0207 (2)
H110.94740.48270.00260.025*
H120.72910.56770.02660.025*
C20.7025 (2)0.48177 (11)0.08139 (6)0.0180 (2)
H210.81210.45480.12200.022*
C30.53376 (19)0.58161 (11)0.11711 (6)0.0170 (2)
H310.61630.66410.13590.020*
C40.4048 (2)0.51893 (11)0.18363 (6)0.0199 (2)
H410.51340.47880.22010.024*
H420.31050.44350.16380.024*
C50.2547 (2)0.61961 (11)0.22686 (6)0.0203 (2)
H510.16470.67200.18940.024*
H520.35070.68540.25490.024*
C60.0959 (2)0.55018 (12)0.28385 (6)0.0213 (2)
H610.01090.47800.25550.026*
C70.0741 (2)0.65233 (13)0.31559 (7)0.0280 (3)
H710.17910.60470.34950.042*
H720.15690.69420.27320.042*
H730.00470.72360.34440.042*
C80.5905 (2)0.35146 (12)0.05142 (7)0.0269 (3)
H810.70220.29500.02500.040*
H820.47060.37600.01560.040*
H830.52720.30000.09440.040*
C90.2233 (3)0.48031 (14)0.34869 (7)0.0315 (3)
H910.11680.43350.38240.047*
H920.30640.54900.37810.047*
H930.32850.41350.32720.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0142 (4)0.0238 (4)0.0268 (4)0.0007 (4)0.0012 (3)0.0068 (3)
O20.0143 (4)0.0267 (4)0.0249 (4)0.0012 (4)0.0002 (3)0.0107 (3)
C10.0180 (6)0.0235 (5)0.0205 (5)0.0002 (5)0.0017 (4)0.0010 (4)
C20.0173 (5)0.0173 (5)0.0196 (5)0.0009 (5)0.0004 (4)0.0016 (4)
C30.0154 (5)0.0171 (5)0.0184 (5)0.0002 (4)0.0002 (4)0.0020 (4)
C40.0210 (6)0.0184 (5)0.0201 (5)0.0009 (5)0.0034 (4)0.0025 (4)
C50.0221 (6)0.0187 (5)0.0203 (5)0.0011 (5)0.0039 (4)0.0014 (4)
C60.0224 (6)0.0216 (5)0.0201 (5)0.0020 (5)0.0045 (5)0.0017 (4)
C70.0268 (7)0.0316 (6)0.0257 (5)0.0043 (6)0.0063 (5)0.0015 (5)
C80.0299 (7)0.0196 (5)0.0312 (6)0.0022 (5)0.0059 (6)0.0045 (5)
C90.0400 (8)0.0301 (6)0.0243 (5)0.0086 (6)0.0079 (6)0.0074 (5)
Geometric parameters (Å, º) top
O1—C11.4271 (15)C5—C61.5327 (16)
O1—H10.844 (19)C5—H510.9900
O2—C31.4366 (14)C5—H520.9900
O2—H20.827 (17)C6—C91.5251 (18)
C1—C21.5243 (15)C6—C71.5274 (17)
C1—H110.9900C6—H611.0000
C1—H120.9900C7—H710.9800
C2—C81.5307 (16)C7—H720.9800
C2—C31.5345 (15)C7—H730.9800
C2—H211.0000C8—H810.9800
C3—C41.5224 (15)C8—H820.9800
C3—H311.0000C8—H830.9800
C4—C51.5295 (15)C9—H910.9800
C4—H410.9900C9—H920.9800
C4—H420.9900C9—H930.9800
C1—O1—H1108.8 (12)C6—C5—H51108.9
C3—O2—H2110.7 (12)C4—C5—H52108.9
O1—C1—C2112.78 (9)C6—C5—H52108.9
O1—C1—H11109.0H51—C5—H52107.7
C2—C1—H11109.0C9—C6—C7110.72 (10)
O1—C1—H12109.0C9—C6—C5111.91 (11)
C2—C1—H12109.0C7—C6—C5110.88 (10)
H11—C1—H12107.8C9—C6—H61107.7
C1—C2—C8108.73 (9)C7—C6—H61107.7
C1—C2—C3111.63 (9)C5—C6—H61107.7
C8—C2—C3112.49 (10)C6—C7—H71109.5
C1—C2—H21107.9C6—C7—H72109.5
C8—C2—H21107.9H71—C7—H72109.5
C3—C2—H21107.9C6—C7—H73109.5
O2—C3—C4107.36 (9)H71—C7—H73109.5
O2—C3—C2110.11 (9)H72—C7—H73109.5
C4—C3—C2112.69 (9)C2—C8—H81109.5
O2—C3—H31108.9C2—C8—H82109.5
C4—C3—H31108.9H81—C8—H82109.5
C2—C3—H31108.9C2—C8—H83109.5
C3—C4—C5114.42 (9)H81—C8—H83109.5
C3—C4—H41108.7H82—C8—H83109.5
C5—C4—H41108.7C6—C9—H91109.5
C3—C4—H42108.7C6—C9—H92109.5
C5—C4—H42108.7H91—C9—H92109.5
H41—C4—H42107.6C6—C9—H93109.5
C4—C5—C6113.40 (9)H91—C9—H93109.5
C4—C5—H51108.9H92—C9—H93109.5
O1—C1—C2—C354.59 (12)C4—C5—C6—C7170.92 (10)
O1—C1—C2—C8179.27 (10)C4—C5—C6—C964.91 (13)
C1—C2—C3—C4178.67 (10)C8—C2—C3—O261.06 (11)
C1—C2—C3—O261.50 (12)C8—C2—C3—C458.78 (12)
C2—C3—C4—C5173.22 (10)O2—C3—C4—C565.37 (12)
C3—C4—C5—C6169.71 (10)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.844 (19)1.812 (19)2.6395 (16)166.4 (16)
O2—H2···O1ii0.827 (17)1.886 (16)2.6809 (14)160.9 (17)
Symmetry codes: (i) x+1, y, z; (ii) x1/2, y+3/2, z.
(II) (R)-4-Benzyl-3-[(2R,3S)-3-hydroxy-2,6-dimethylheptanoyl]-1,3-oxazolidin-2-one top
Crystal data top
C19H27NO4F(000) = 360
Mr = 333.42Dx = 1.143 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 2875 reflections
a = 11.459 (3) Åθ = 2.8–24.7°
b = 5.7077 (13) ŵ = 0.08 mm1
c = 15.247 (3) ÅT = 105 K
β = 103.827 (3)°Flat needle, colourless
V = 968.4 (4) Å31.54 × 0.13 × 0.04 mm
Z = 2
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2047 independent reflections
Radiation source: fine-focus sealed tube1823 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
Detector resolution: 8.3 pixels mm-1θmax = 25.8°, θmin = 1.8°
Sets of exposures each taken over 0.5° ω rotation scansh = 1412
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
k = 66
Tmin = 0.837, Tmax = 0.997l = 1818
7434 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)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0465P)2 + 0.1669P]
where P = (Fo2 + 2Fc2)/3
2047 reflections(Δ/σ)max < 0.001
223 parametersΔρmax = 0.13 e Å3
1 restraintΔρmin = 0.25 e Å3
Crystal data top
C19H27NO4V = 968.4 (4) Å3
Mr = 333.42Z = 2
Monoclinic, P21Mo Kα radiation
a = 11.459 (3) ŵ = 0.08 mm1
b = 5.7077 (13) ÅT = 105 K
c = 15.247 (3) Å1.54 × 0.13 × 0.04 mm
β = 103.827 (3)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2047 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
1823 reflections with I > 2σ(I)
Tmin = 0.837, Tmax = 0.997Rint = 0.031
7434 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0341 restraint
wR(F2) = 0.087H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.13 e Å3
2047 reflectionsΔρmin = 0.25 e Å3
223 parameters
Special details top

Experimental. Very difficult crystals, easily bent and split along the needle. Crystal mounted along the ϕ spindle axis

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
O10.87786 (12)0.4551 (3)0.44852 (9)0.0254 (4)
O20.86511 (14)0.0283 (3)0.54877 (9)0.0251 (3)
H20.940 (2)0.026 (6)0.5564 (16)0.038*
O30.49699 (12)0.5192 (3)0.46446 (9)0.0238 (3)
O40.61832 (12)0.4959 (3)0.60301 (9)0.0244 (3)
N10.69270 (14)0.4801 (3)0.47262 (10)0.0218 (4)
C10.81682 (18)0.4440 (4)0.50355 (14)0.0217 (5)
C20.86596 (19)0.3801 (4)0.60155 (15)0.0216 (5)
H210.82550.48070.63920.026*
C30.8321 (2)0.1211 (4)0.61377 (14)0.0234 (5)
H310.74250.11500.60220.028*
C40.8814 (2)0.0300 (4)0.70929 (13)0.0279 (5)
H410.97020.02510.72150.033*
H420.85280.13260.71280.033*
C50.8457 (2)0.1757 (4)0.78304 (15)0.0301 (5)
H510.89350.32210.79190.036*
H520.76000.21960.76240.036*
C60.8646 (3)0.0488 (5)0.87344 (16)0.0430 (7)
H610.94560.02700.88740.052*
C70.8588 (3)0.2198 (6)0.94957 (17)0.0536 (8)
H710.87410.13501.00710.080*
H720.77890.29170.93760.080*
H730.91970.34210.95280.080*
C81.00082 (18)0.4275 (4)0.62960 (14)0.0264 (5)
H811.02920.40880.69510.040*
H821.01690.58780.61260.040*
H831.04300.31640.59900.040*
C90.7694 (4)0.1403 (7)0.8686 (2)0.0775 (12)
H910.77110.24740.81870.116*
H920.69000.06720.85850.116*
H930.78610.22790.92550.116*
C100.60599 (17)0.4963 (4)0.52244 (13)0.0216 (4)
C110.64050 (18)0.5352 (4)0.37677 (13)0.0219 (5)
H1110.67180.42610.33640.026*
C120.50794 (18)0.4867 (5)0.37205 (13)0.0251 (5)
H1210.45570.59800.33060.030*
H1220.48600.32490.35110.030*
C130.6643 (2)0.7912 (4)0.35562 (14)0.0235 (5)
H1310.61640.89590.38510.028*
H1320.75040.82800.38020.028*
C140.6314 (2)0.8345 (4)0.25443 (14)0.0253 (5)
C150.7081 (2)0.7539 (5)0.20272 (16)0.0370 (6)
H1510.77950.67230.23080.044*
C160.6803 (3)0.7930 (6)0.10996 (17)0.0468 (7)
H1610.73270.73640.07490.056*
C170.5775 (3)0.9129 (5)0.06833 (16)0.0430 (7)
H1710.55980.94240.00520.052*
C180.5012 (2)0.9891 (6)0.11928 (15)0.0407 (6)
H1810.42941.06920.09090.049*
C190.5278 (2)0.9502 (4)0.21213 (15)0.0313 (5)
H1910.47411.00390.24650.038*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0262 (8)0.0237 (9)0.0289 (8)0.0018 (7)0.0116 (6)0.0007 (7)
O20.0254 (7)0.0202 (8)0.0308 (8)0.0005 (7)0.0087 (6)0.0044 (7)
O30.0210 (7)0.0216 (8)0.0295 (7)0.0019 (7)0.0075 (6)0.0017 (7)
O40.0264 (7)0.0214 (8)0.0277 (7)0.0030 (7)0.0111 (6)0.0012 (7)
N10.0215 (8)0.0209 (9)0.0238 (8)0.0027 (8)0.0074 (7)0.0025 (9)
C10.0229 (11)0.0135 (11)0.0289 (11)0.0000 (8)0.0068 (9)0.0002 (9)
C20.0225 (11)0.0170 (11)0.0263 (11)0.0011 (9)0.0075 (9)0.0007 (9)
C30.0245 (11)0.0177 (11)0.0294 (12)0.0003 (9)0.0093 (9)0.0019 (9)
C40.0333 (12)0.0211 (12)0.0301 (11)0.0016 (10)0.0092 (9)0.0037 (10)
C50.0344 (13)0.0246 (12)0.0315 (12)0.0003 (10)0.0086 (10)0.0003 (10)
C60.0579 (17)0.0411 (17)0.0329 (13)0.0100 (14)0.0166 (12)0.0088 (12)
C70.076 (2)0.054 (2)0.0322 (14)0.0045 (17)0.0153 (14)0.0022 (14)
C80.0263 (12)0.0227 (13)0.0303 (11)0.0003 (9)0.0070 (9)0.0007 (10)
C90.148 (4)0.0402 (19)0.063 (2)0.022 (2)0.062 (2)0.0025 (17)
C100.0246 (10)0.0119 (10)0.0303 (11)0.0010 (10)0.0103 (8)0.0015 (10)
C110.0244 (10)0.0191 (11)0.0228 (10)0.0011 (9)0.0066 (8)0.0001 (9)
C120.0280 (11)0.0219 (11)0.0257 (10)0.0026 (10)0.0067 (8)0.0007 (10)
C130.0231 (11)0.0216 (12)0.0254 (11)0.0023 (9)0.0051 (9)0.0002 (9)
C140.0293 (12)0.0208 (12)0.0257 (11)0.0046 (9)0.0065 (10)0.0014 (9)
C150.0366 (14)0.0433 (16)0.0329 (13)0.0022 (12)0.0118 (11)0.0027 (12)
C160.0570 (18)0.0523 (19)0.0367 (14)0.0024 (15)0.0225 (13)0.0000 (14)
C170.0638 (18)0.0391 (17)0.0260 (12)0.0017 (14)0.0105 (12)0.0038 (11)
C180.0538 (15)0.0330 (14)0.0312 (11)0.0110 (14)0.0018 (11)0.0055 (12)
C190.0406 (13)0.0248 (13)0.0289 (11)0.0034 (11)0.0090 (10)0.0010 (10)
Geometric parameters (Å, º) top
O1—C11.216 (2)C7—H730.9800
O2—C31.425 (3)C8—H810.9800
O2—H20.84 (3)C8—H820.9800
O3—C101.353 (2)C8—H830.9800
O3—C121.456 (2)C9—H910.9800
O4—C101.203 (2)C9—H920.9800
N1—C101.390 (3)C9—H930.9800
N1—C11.403 (3)C11—C121.529 (3)
N1—C111.475 (2)C11—C131.534 (3)
C1—C21.510 (3)C11—H1111.0000
C2—C81.526 (3)C12—H1210.9900
C2—C31.551 (3)C12—H1220.9900
C2—H211.0000C13—C141.518 (3)
C3—C41.522 (3)C13—H1310.9900
C3—H311.0000C13—H1320.9900
C4—C51.531 (3)C14—C191.377 (3)
C4—H410.9900C14—C151.392 (3)
C4—H420.9900C15—C161.391 (4)
C5—C61.526 (3)C15—H1510.9500
C5—H510.9900C16—C171.379 (4)
C5—H520.9900C16—H1610.9500
C6—C91.523 (5)C17—C181.372 (4)
C6—C71.530 (4)C17—H1710.9500
C6—H611.0000C18—C191.393 (3)
C7—H710.9800C18—H1810.9500
C7—H720.9800C19—H1910.9500
C3—O2—H2109.1 (19)H81—C8—H83109.5
C10—O3—C12109.90 (15)H82—C8—H83109.5
C10—N1—C1128.74 (16)C6—C9—H91109.5
C10—N1—C11110.70 (16)C6—C9—H92109.5
C1—N1—C11120.20 (15)H91—C9—H92109.5
O1—C1—N1117.70 (18)C6—C9—H93109.5
O1—C1—C2123.75 (19)H91—C9—H93109.5
N1—C1—C2118.45 (17)H92—C9—H93109.5
C1—C2—C8110.35 (17)O4—C10—O3122.17 (17)
C1—C2—C3107.70 (18)O4—C10—N1129.27 (18)
C8—C2—C3113.63 (18)O3—C10—N1108.55 (16)
C1—C2—H21108.3N1—C11—C1299.85 (15)
C8—C2—H21108.3N1—C11—C13111.18 (18)
C3—C2—H21108.3C12—C11—C13112.78 (19)
O2—C3—C4111.18 (19)N1—C11—H111110.9
O2—C3—C2111.79 (17)C12—C11—H111110.9
C4—C3—C2113.23 (19)C13—C11—H111110.9
O2—C3—H31106.7O3—C12—C11104.23 (15)
C4—C3—H31106.7O3—C12—H121110.9
C2—C3—H31106.7C11—C12—H121110.9
C3—C4—C5114.44 (19)O3—C12—H122110.9
C3—C4—H41108.6C11—C12—H122110.9
C5—C4—H41108.6H121—C12—H122108.9
C3—C4—H42108.6C14—C13—C11110.80 (18)
C5—C4—H42108.6C14—C13—H131109.5
H41—C4—H42107.6C11—C13—H131109.5
C6—C5—C4113.6 (2)C14—C13—H132109.5
C6—C5—H51108.8C11—C13—H132109.5
C4—C5—H51108.8H131—C13—H132108.1
C6—C5—H52108.8C19—C14—C15118.9 (2)
C4—C5—H52108.8C19—C14—C13122.1 (2)
H51—C5—H52107.7C15—C14—C13119.0 (2)
C9—C6—C5110.3 (2)C16—C15—C14120.0 (3)
C9—C6—C7109.2 (2)C16—C15—H151120.0
C5—C6—C7111.1 (2)C14—C15—H151120.0
C9—C6—H61108.7C17—C16—C15120.7 (3)
C5—C6—H61108.7C17—C16—H161119.7
C7—C6—H61108.7C15—C16—H161119.7
C6—C7—H71109.5C18—C17—C16119.1 (2)
C6—C7—H72109.5C18—C17—H171120.4
H71—C7—H72109.5C16—C17—H171120.4
C6—C7—H73109.5C17—C18—C19120.7 (2)
H71—C7—H73109.5C17—C18—H181119.7
H72—C7—H73109.5C19—C18—H181119.7
C2—C8—H81109.5C14—C19—C18120.5 (2)
C2—C8—H82109.5C14—C19—H191119.7
H81—C8—H82109.5C18—C19—H191119.7
C2—C8—H83109.5
O1—C1—C2—C3102.1 (2)C1—N1—C10—O3176.8 (2)
O1—C1—C2—C822.5 (3)C10—N1—C1—O1174.0 (2)
C1—C2—C3—C4177.37 (17)C11—N1—C1—O11.5 (3)
C1—C2—C3—O250.9 (2)N1—C1—C2—C8161.17 (18)
C2—C3—C4—C555.4 (2)C8—C2—C3—O271.7 (2)
C3—C4—C5—C6163.7 (2)C8—C2—C3—C454.8 (2)
C4—C5—C6—C7165.4 (2)O2—C3—C4—C5177.72 (19)
C4—C5—C6—C973.4 (3)C12—O3—C10—O4173.5 (2)
N1—C1—C2—C374.3 (2)C1—N1—C10—O44.5 (4)
C11—N1—C1—C2178.0 (2)C11—N1—C10—O4168.6 (2)
C10—N1—C1—C29.5 (3)C10—N1—C11—C1397.2 (2)
C1—N1—C11—C12164.25 (19)C13—C11—C12—O393.1 (2)
N1—C11—C12—O325.0 (2)C12—C11—C13—C1479.4 (2)
C11—C12—O3—C1021.4 (2)C19—C14—C15—C160.7 (4)
C12—O3—C10—N17.6 (2)C13—C14—C15—C16179.6 (2)
O3—C10—N1—C1110.2 (2)C14—C15—C16—C170.6 (5)
C10—N1—C11—C1222.0 (2)C15—C16—C17—C181.5 (5)
C1—N1—C11—C1376.5 (2)C16—C17—C18—C191.2 (4)
N1—C11—C13—C14169.41 (17)C15—C14—C19—C181.0 (4)
C11—C13—C14—C1575.9 (3)C13—C14—C19—C18179.3 (2)
C11—C13—C14—C19103.9 (3)C17—C18—C19—C140.0 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.84 (3)2.11 (3)2.937 (2)170 (2)
C12—H122···O4ii0.992.423.217 (3)137
C8—H83···O1i0.982.433.379 (3)162
Symmetry codes: (i) x+2, y1/2, z+1; (ii) x+1, y1/2, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC9H20O2C19H27NO4
Mr160.25333.42
Crystal system, space groupOrthorhombic, P212121Monoclinic, P21
Temperature (K)105105
a, b, c (Å)5.964 (2), 9.777 (4), 17.469 (6)11.459 (3), 5.7077 (13), 15.247 (3)
α, β, γ (°)90, 90, 9090, 103.827 (3), 90
V3)1018.6 (6)968.4 (4)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.070.08
Crystal size (mm)1.85 × 0.14 × 0.131.54 × 0.13 × 0.04
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Bruker APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2007)
Multi-scan
(SADABS; Bruker, 2007)
Tmin, Tmax0.851, 0.9900.837, 0.997
No. of measured, independent and
observed [I > 2σ(I)] reflections
9215, 1487, 1387 7434, 2047, 1823
Rint0.0260.031
(sin θ/λ)max1)0.6720.613
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.074, 1.04 0.034, 0.087, 1.04
No. of reflections14872047
No. of parameters109223
No. of restraints01
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.23, 0.140.13, 0.25

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Selected torsion angles (º) for (I) top
O1—C1—C2—C354.59 (12)C2—C3—C4—C5173.22 (10)
O1—C1—C2—C8179.27 (10)C3—C4—C5—C6169.71 (10)
C1—C2—C3—C4178.67 (10)C4—C5—C6—C7170.92 (10)
C1—C2—C3—O261.50 (12)C4—C5—C6—C964.91 (13)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.844 (19)1.812 (19)2.6395 (16)166.4 (16)
O2—H2···O1ii0.827 (17)1.886 (16)2.6809 (14)160.9 (17)
Symmetry codes: (i) x+1, y, z; (ii) x1/2, y+3/2, z.
Selected torsion angles (º) for (II) top
O1—C1—C2—C3102.1 (2)C1—N1—C11—C12164.25 (19)
O1—C1—C2—C822.5 (3)N1—C11—C12—O325.0 (2)
C1—C2—C3—C4177.37 (17)C11—C12—O3—C1021.4 (2)
C1—C2—C3—O250.9 (2)C12—O3—C10—N17.6 (2)
C2—C3—C4—C555.4 (2)O3—C10—N1—C1110.2 (2)
C3—C4—C5—C6163.7 (2)C10—N1—C11—C1222.0 (2)
C4—C5—C6—C7165.4 (2)C1—N1—C11—C1376.5 (2)
C4—C5—C6—C973.4 (3)N1—C11—C13—C14169.41 (17)
N1—C1—C2—C374.3 (2)C11—C13—C14—C1575.9 (3)
C11—N1—C1—C2178.0 (2)C11—C13—C14—C19103.9 (3)
C10—N1—C1—C29.5 (3)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.84 (3)2.11 (3)2.937 (2)170 (2)
C12—H122···O4ii0.992.423.217 (3)137.4
C8—H83···O1i0.982.433.379 (3)162.1
Symmetry codes: (i) x+2, y1/2, z+1; (ii) x+1, y1/2, z+1.
 

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