6-[Bis(ethoxycarbonyl)methyl]-6-deoxy-1,2;3,4-di-O-isopropyl­idene-d-galacto­pyran­ose

Doboszewski, B.; Silva, P.R. da; Nazarenko, A.Y.; Nemykin, V.N.

doi:10.1107/S1600536810046921

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Pages o3217-o3218

https://doi.org/10.1107/S1600536810046921

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6-[Bis(ethoxycarbonyl)methyl]-6-deoxy-1,2;3,4-di-O-isopropylidene-D-galactopyranose

Bogdan Doboszewski,^a Paulo R. da Silva,^a Alexander Y. Nazarenko ^b ^* and Victor N. Nemykin ^c

^aDepartamento de Química, Universidade Federal Rural de Pernambuco, 52171-900 Recife, PE, Brazil, ^bChemistry Department, State University of New York, College at Buffalo, 1300 Elmwood Ave, Buffalo, NY 14222-1095, USA, and ^cDepartment of Chemistry & Biochemistry, University of Minnesota Duluth, Duluth, Minnesota 55812-2496, USA
^*Correspondence e-mail: nazareay@buffalostate.edu

(Received 9 November 2010; accepted 12 November 2010; online 17 November 2010)

The title compound, C₁₉H₃₀O₉, was prepared by substitution at the C6 position in 1,2;3,4-di-O-isopropylidene-6-O-trifluoromethanesulfonyl-D-galactose using sodium ethoxymalonate in dimethylformamide. The conformation is skew-boat ⁰S₂, slightly distorted towards boat B_2,5. The inflexible pyranose structure makes the title compound a suitable intermediate for further synthetic work by keeping stereogenic carbon atoms safe from inversion. Several short intramolecular C—H⋯ O contacts may stabilize the conformation of the molecule. Intermolecular C—H⋯O interactions also occur.

Related literature

For syntheses of this and similar compounds, see: Bouhlal et al. (2001 ); Doboszewski et al. (1987 ); Honeyman & Stening (1958 ); Sugihara et al. (1963 ); Tipson (1953 ); Cipolla et al. (1996 ). For the structures of diisopropylidene-galactopyranose and related compounds, see: Krajewski et al. (1990 , 1994 ); Coutrot et al. (2001 ); Weaver et al. (2004 , 2006 ); Boeyens et al. (1978 ); Berces et al. (2001 ). For conformations of small rings, see: Schwarz (1973 ); Cremer & Pople (1975 ); Boeyens (1978 ); Hill & Reilly (2007 ); Köll et al. (1994 ). For analysis of absolute structure, see: Flack (1983 ); Hooft et al. (2008 ).

Experimental

Crystal data

C₁₉H₃₀O₉
M_r = 402.43
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.3287 (4) Å
b = 10.8895 (4) Å
c = 23.7706 (16) Å
V = 2155.9 (2) Å³
Z = 4
Cu Kα radiation
μ = 0.83 mm⁻¹
T = 292 K
0.38 × 0.26 × 0.21 mm

Data collection

Rigaku R-AXIS RAPID II imaging plate diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi,1995 ) T_min = 0.822, T_max = 0.840
9353 measured reflections
3745 independent reflections
2824 reflections with I > 2σ(I)
R_int = 0.075

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.096
S = 1.02
3745 reflections
275 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.15 e Å⁻³
Absolute structure: Flack (1983), 1607 Friedel pairs
Flack parameter: 0.06 (18)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O9ⁱ	0.98	2.43	3.381 (3)	163
C5—H5A⋯O7	1.01	2.59	3.185 (3)	117
C8—H8B⋯O7ⁱ	1.03	2.56	3.577 (3)	169
C12—H12A⋯O5	1.02	2.42	2.811 (3)	102
C13—H13A⋯O1	0.96	2.43	2.814 (3)	103
C16—H16B⋯O1ⁱⁱ	0.99	2.51	3.422 (3)	153
Symmetry codes: (i) x-1, y, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear-SM Expert (Rigaku, 2009 ); cell refinement: HKL-2000 (Otwinowski & Minor, 1997 ); data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: PLATON (Spek, 2009).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810046921/zl2327sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810046921/zl2327Isup2.hkl

checkCIF report

Comment top

The title compound is an intermediate for the synthesis of a wide range of chain-extended galactopyranoses, which in turn are considered as precursors of chiral α-hydroxycarboxylic acids. The stereogenic atom C5 is retained in the target compounds. Knowledge of exact geometry of the intermediate is helpful for better understanding of upcoming steps in this ongoing synthetic project.

To realise these objectives we (BD & PRS) have prepared the title compound by substitution at the C6 position in 1,2;3,4-di-O-isopropylidene-6-O-trifluoromethanesulfonyl-D-galactose using sodium ethoxymalonate. Substitutions at this atom in diisopropylidene-galactose are rather difficult and require prolonged reaction times and/or elevated temperatures (Tipson, 1953, Honeyman & Stening, 1958, Sugihara et al., 1963, Bouhlal et al., 2001). Howeever, by using the best available leaving group, a trifluoromethanesulfonate, smooth nucleophilic substitution can been accomplished in less than 10 min (Doboszewski et al., 1987).

The absolute structure of 6-deoxy-6-(diethylmalonyl)-1,2;3,4-di-O -isopropylidene-D-galactopyranose is certain from the synthetic route which does not affect asymmetric atoms of the starting compound. Nevertheless, we preferred to receive a direct experimental confirmation using X-ray diffractometry data. Because there are no heavy atoms in a chiral molecule of title compound, Cu Kα radiation was necessary for determination of the absolute structure.

In the crystal structure of title compound (Fig.1), all bond lengths and bond angles have standard dimensions.

Fig. 2 shows that the pyranose ring adopts a skew-boat with atoms C1, C3, C4, and C5 being within 0.03–0.08 Å from their mean plane, and O1 and C2 atoms being at 0.633 (2) and -0.557 (2) Å, respectively. Such conformation is named ^OS₂ in the IUPAC notation (Schwarz, 1973). A quantitative analysis of the ring conformations in the titlw compound was performed using the method of Cremer and Pople (Cremer & Pople, 1975, Boeyens, 1978) for the calculation of parameters of puckering. The polar parameters for the pyranose ring are Q = 0.639 (2) Å, Φ = 325.1 (2)°, and θ = 80.3 (2)°. These suggest the conformation as skew-boat ⁰S₂ (Φ = 330°, θ = 90°), slightly distorted towards boat B_2,5, (Φ = 300°, θ = 90°); the same conformation is designated as a twist-boat ^OT₂ when using the Boeyenes nomenclature. This conformation is similar to many other known galactopyranoses with two substituent isopropylidene rings (see, for example, POCSUV (Krajewski et al., 1994): Q = 0.632 (5) Å, θ = 82.8 (5)°,Φ = 327.4 (4)°; JERJIUL (Krajewski et al., 1990): Q = 0.631 (5) Å, θ = 79.7 (5)°, Φ = 324.9 (5)°; ICALED (Coutrot et al., 2001): Q = 0.646 (4) Å, θ = 83.9 (4)°, Φ = 334.2 (3)°; BIHZUO (Weaver et al., 2004): Q = 0.661 (2) Å, θ = 81.3 (2)°, Φ = 327.1 (2)°; ADXPOP (Boeyens, Rathbone & Woolard,1978): Q = 0.65 Å, Φ = 329°, θ = 81°). All conformations of substituted compounds are radically different from the chair conformation of unsubstituted α -D-galactopyranose. This is caused by the presence of the two isopropylidene substituents that make the geometry of the pyranose ring more rigid and less sensitive towards any effects of substituents at the remaining C5 position. A detailed discussion of terminology and different puckering coordinates being used to describe six-membered non-aromatic cycles can be found in Hill & Reilly (2007) and Köll et al. (1994).

The same approach yielded the parameters of puckering Q(2) = 0.279 (2) Å, Φ = 283.3 (4)° and Q(2) = 0.234 (2) Å, Φ = 177.1 (7)° for the 1,2- and 3,4- isopropylidene rings. These values correspond to the envelope conformations ⁴E (Φ = 288°) and E₁ (Φ = 180°) with atoms O3 and O4 being out of their corresponding planes by 0.426 (2) and 0.357 (2) Å correspondingly (Fig. 3 and 4). All other atoms in both five-membered rings are located within 0.01 Å from their mean planes.

No classic hydrogen bonds are possible for the title compound. However, several short C—H··· O contacts were detected that possibly stabilize the existing conformation of the molecule (Table 1).

The inflexible pyranose structure makes the title compound a suitable intermediate for further synthetic work by keeping the stereogenic carbon atoms C1—C5 safe from inversion. For the same reason, it is very probable that in solution this molecule will keep almost the same geometry as in the molecular crystal.

Related literature top

For syntheses of this and similar compounds, see: Bouhlal et al. (2001); Doboszewski et al. (1987); Honeyman & Stening (1958); Sugihara et al. (1963); Tipson (1953); Cipolla et al. (1996). For the structures of diisopropylidene-galactopyranose and related compounds, see: Krajewski et al. (1990, 1994); Coutrot et al. (2001); Weaver et al. (2004, 2006); Boeyens et al. (1978); Berces et al. (2001). For conformations of small rings, see: Schwarz (1973); Cremer & Pople (1975); Boeyens (1978); Hill & Reilly (2007); Köll et al. (1994). For analysis of absolute structure, see: Flack (1983); Hooft et al. (2008).

Experimental top

Synthesis of the title compound was accomplished similar to previuosly published fluorination reaction (Doboszewski et al., 1987). We treated 1,2;3,4-di-O-isopropylidene-6-O-trifluoromethanesulfonyl-D- galactose with sodium ethoxymalonate in dimethylformamide at 333 K; the title compound was isolated in 80% yield (Figure 5). The compound is identical to previously obtained via a free-radical process in low yield (Cipolla et al., 1996). Spontaneous crystallization from a hexane-ethyl acetate system yielded colourless crystals suitable for single-crystal diffractometry (m.p. 331–334 K).

Structure description top

In the crystal structure of title compound (Fig.1), all bond lengths and bond angles have standard dimensions.

No classic hydrogen bonds are possible for the title compound. However, several short C—H··· O contacts were detected that possibly stabilize the existing conformation of the molecule (Table 1).

For syntheses of this and similar compounds, see: Bouhlal et al. (2001); Doboszewski et al. (1987); Honeyman & Stening (1958); Sugihara et al. (1963); Tipson (1953); Cipolla et al. (1996). For the structures of diisopropylidene-galactopyranose and related compounds, see: Krajewski et al. (1990, 1994); Coutrot et al. (2001); Weaver et al. (2004, 2006); Boeyens et al. (1978); Berces et al. (2001). For conformations of small rings, see: Schwarz (1973); Cremer & Pople (1975); Boeyens (1978); Hill & Reilly (2007); Köll et al. (1994). For analysis of absolute structure, see: Flack (1983); Hooft et al. (2008).

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku, 2009); cell refinement: HKL-2000 (Otwinowski & Minor, 1997); data reduction: CrystalClear-SM Expert (Rigaku, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1999); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitary radius.
	Fig. 2. Conformation of the six-membered ring: mean plane drawn through C1—C3—C4—C5.
	Fig. 3. Conformation of the five-membered isopropylidene ring: plane through C1 C2 C6 O2.
	Fig. 4. Conformation of the five-membered isopropylidene ring: plane through C3 C9 O5 C4.
	Fig. 5. Synthetic route towards the title compound.

6-[Bis(ethoxycarbonyl)methyl]-6-deoxy-1,2;3,4-di-O-isopropylidene- D-galactopyranose top

Crystal data top

C₁₉H₃₀O₉	D_x = 1.240 Mg m⁻³
M_r = 402.43	Melting point: 322 K
Orthorhombic, P2₁2₁2₁	Cu Kα radiation, λ = 1.54187 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9579 reflections
a = 8.3287 (4) Å	θ = 6.7–68.2°
b = 10.8895 (4) Å	µ = 0.83 mm⁻¹
c = 23.7706 (16) Å	T = 292 K
V = 2155.9 (2) Å³	Prism, colourless
Z = 4	0.38 × 0.26 × 0.21 mm
F(000) = 864

Data collection top

Rigaku R-AXIS RAPID II imaging plate diffractometer	3745 independent reflections
Radiation source: fine-focus sealed tube	2824 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.075
Detector resolution: 10 pixels mm^-1	θ_max = 66.5°, θ_min = 6.7°
ω scans	h = −6→9
Absorption correction: multi-scan (ABSCOR; Higashi,1995)	k = −12→10
T_min = 0.822, T_max = 0.840	l = −28→19
9353 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.040	w = 1/[σ²(F_o²) + (0.0285P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.096	(Δ/σ)_max < 0.001
S = 1.02	Δρ_max = 0.19 e Å⁻³
3745 reflections	Δρ_min = −0.15 e Å⁻³
275 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0057 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1607 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.06 (18)

Crystal data top

C₁₉H₃₀O₉	V = 2155.9 (2) Å³
M_r = 402.43	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 8.3287 (4) Å	µ = 0.83 mm⁻¹
b = 10.8895 (4) Å	T = 292 K
c = 23.7706 (16) Å	0.38 × 0.26 × 0.21 mm

Data collection top

Rigaku R-AXIS RAPID II imaging plate diffractometer	3745 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi,1995)	2824 reflections with I > 2σ(I)
T_min = 0.822, T_max = 0.840	R_int = 0.075
9353 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.096	Δρ_max = 0.19 e Å⁻³
S = 1.02	Δρ_min = −0.15 e Å⁻³
3745 reflections	Absolute structure: Flack (1983), 1607 Friedel pairs
275 parameters	Absolute structure parameter: 0.06 (18)
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq
O1	0.30842 (18)	0.05824 (11)	0.37716 (6)	0.0531 (4)
O2	0.2263 (2)	0.25329 (12)	0.35151 (6)	0.0653 (5)
O3	0.2044 (2)	0.30221 (12)	0.44385 (6)	0.0646 (5)
O4	0.0989 (2)	−0.00622 (15)	0.48415 (7)	0.0747 (5)
O5	0.3563 (2)	−0.07330 (14)	0.48515 (7)	0.0817 (6)
O6	0.6685 (2)	0.16820 (13)	0.27264 (7)	0.0718 (5)
O7	0.7237 (2)	0.22413 (15)	0.36113 (7)	0.0852 (6)
O8	0.7062 (2)	−0.17738 (13)	0.31233 (6)	0.0666 (5)
O9	0.8976 (2)	−0.03812 (18)	0.32008 (11)	0.1155 (9)
C1	0.1819 (3)	0.14252 (17)	0.37891 (9)	0.0523 (6)
H1A	0.088 (2)	0.1070 (8)	0.3597 (4)	0.063*
C2	0.1329 (3)	0.18443 (17)	0.43770 (9)	0.0573 (6)
H2A	0.012 (3)	0.1918 (2)	0.43999 (11)	0.069*
C3	0.1939 (3)	0.10213 (19)	0.48485 (10)	0.0600 (6)
H3A	0.1836 (4)	0.1456 (10)	0.5227 (8)	0.072*
C4	0.3665 (3)	0.0557 (2)	0.47632 (9)	0.0566 (6)
H4A	0.4367 (16)	0.0921 (8)	0.5044 (6)	0.068*
C5	0.4315 (3)	0.0817 (2)	0.41783 (9)	0.0490 (5)
H5A	0.4630 (7)	0.1708 (18)	0.41554 (10)	0.059*
C6	0.2124 (3)	0.35512 (18)	0.38911 (9)	0.0580 (6)
C7	0.3592 (3)	0.4335 (2)	0.38497 (12)	0.0860 (10)
H7A	0.3572 (11)	0.4945 (14)	0.4142 (7)	0.129*
H7B	0.3615 (12)	0.4733 (15)	0.3489 (6)	0.129*
H7C	0.4532 (15)	0.3831 (8)	0.3892 (8)	0.129*
C8	0.0607 (3)	0.4254 (2)	0.37542 (11)	0.0742 (8)
H8A	0.0457 (11)	0.4951 (13)	0.4040 (6)	0.111*
H8B	−0.0360 (13)	0.3671 (8)	0.3773 (7)	0.111*
H8C	0.0694 (9)	0.4617 (14)	0.3357 (6)	0.111*
C9	0.1971 (3)	−0.1063 (2)	0.49989 (10)	0.0657 (7)
C10	0.1486 (5)	−0.2177 (2)	0.46606 (14)	0.1124 (13)
H10A	0.034 (2)	−0.2405 (13)	0.4754 (7)	0.169*
H10B	0.222 (2)	−0.2886 (14)	0.4756 (8)	0.169*
H10C	0.157 (3)	−0.1985 (8)	0.4246 (7)	0.169*
C11	0.1883 (4)	−0.1306 (3)	0.56235 (11)	0.0901 (10)
H11A	0.0735 (17)	−0.1545 (17)	0.5730 (2)	0.135*
H11B	0.221 (2)	−0.0531 (13)	0.5838 (3)	0.135*
H11C	0.265 (2)	−0.2007 (15)	0.5725 (2)	0.135*
C12	0.5762 (3)	0.00309 (19)	0.40257 (9)	0.0557 (6)
H12A	0.5494 (4)	−0.0868 (13)	0.40954 (15)	0.067*
H12B	0.6699 (14)	0.0260 (3)	0.4279 (4)	0.067*
C13	0.6261 (3)	0.01977 (16)	0.34089 (9)	0.0510 (6)
H13A	0.535 (2)	0.0017 (4)	0.3179 (5)	0.061*
C14	0.6788 (3)	0.1493 (2)	0.32781 (11)	0.0585 (6)
C15	0.7163 (4)	0.2883 (2)	0.25156 (13)	0.0870 (10)
H15A	0.826 (2)	0.3111 (5)	0.2665 (3)	0.104*
H15B	0.6368 (15)	0.3532 (13)	0.2641 (3)	0.104*
C16	0.7196 (4)	0.2807 (2)	0.18966 (12)	0.0887 (10)
H16A	0.799 (2)	0.2184 (16)	0.1779 (2)	0.133*
H16B	0.750 (2)	0.3614 (13)	0.1739 (3)	0.133*
H16C	0.6122 (18)	0.2572 (17)	0.1757 (3)	0.133*
C17	0.7604 (3)	−0.0665 (2)	0.32388 (10)	0.0608 (6)
C18	0.8256 (3)	−0.2666 (2)	0.29360 (12)	0.0725 (8)
H18A	0.9058 (14)	−0.2830 (3)	0.3248 (5)	0.087*
H18B	0.8859 (11)	−0.2336 (6)	0.2598 (5)	0.087*
C19	0.7401 (4)	−0.3825 (2)	0.27835 (11)	0.0828 (10)
H19A	0.6860 (18)	−0.4159 (10)	0.3119 (5)	0.124*
H19B	0.8182 (11)	−0.4430 (10)	0.2641 (7)	0.124*
H19C	0.6597 (18)	−0.3651 (4)	0.2490 (6)	0.124*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0620 (10)	0.0461 (7)	0.0511 (9)	0.0023 (8)	−0.0101 (7)	−0.0076 (7)
O2	0.0976 (13)	0.0470 (8)	0.0515 (9)	0.0008 (8)	0.0044 (9)	0.0014 (6)
O3	0.0955 (13)	0.0472 (8)	0.0510 (9)	0.0018 (9)	−0.0093 (9)	−0.0041 (7)
O4	0.0744 (13)	0.0687 (10)	0.0811 (13)	−0.0030 (10)	0.0129 (9)	0.0232 (9)
O5	0.0809 (13)	0.0615 (9)	0.1028 (14)	0.0083 (10)	0.0273 (11)	0.0349 (9)
O6	0.0982 (15)	0.0526 (8)	0.0645 (11)	−0.0142 (9)	0.0074 (10)	0.0135 (8)
O7	0.1065 (16)	0.0676 (10)	0.0814 (13)	−0.0359 (11)	0.0086 (12)	−0.0092 (9)
O8	0.0630 (11)	0.0515 (8)	0.0854 (12)	−0.0037 (9)	0.0082 (10)	−0.0091 (8)
O9	0.0547 (12)	0.0826 (12)	0.209 (3)	−0.0130 (11)	0.0071 (14)	−0.0325 (14)
C1	0.0597 (15)	0.0464 (11)	0.0508 (13)	−0.0018 (12)	−0.0106 (12)	−0.0010 (9)
C2	0.0730 (18)	0.0486 (12)	0.0504 (14)	0.0037 (12)	0.0039 (12)	−0.0024 (10)
C3	0.0764 (18)	0.0570 (12)	0.0466 (14)	0.0017 (14)	0.0079 (13)	0.0032 (10)
C4	0.0679 (17)	0.0551 (12)	0.0467 (13)	−0.0024 (13)	−0.0017 (12)	0.0068 (11)
C5	0.0588 (15)	0.0430 (10)	0.0452 (13)	−0.0078 (11)	−0.0057 (11)	0.0016 (9)
C6	0.0759 (18)	0.0446 (11)	0.0534 (14)	0.0025 (13)	−0.0021 (13)	0.0002 (10)
C7	0.087 (2)	0.0612 (15)	0.110 (2)	−0.0130 (16)	−0.0115 (17)	0.0115 (15)
C8	0.0827 (19)	0.0598 (14)	0.0800 (19)	0.0081 (15)	−0.0057 (14)	0.0083 (13)
C9	0.0756 (19)	0.0581 (13)	0.0635 (16)	0.0010 (14)	0.0195 (15)	0.0125 (11)
C10	0.146 (4)	0.0824 (19)	0.108 (3)	−0.020 (2)	0.013 (2)	−0.0156 (18)
C11	0.109 (2)	0.0972 (19)	0.0644 (17)	0.015 (2)	0.0238 (17)	0.0259 (15)
C12	0.0600 (15)	0.0517 (11)	0.0555 (15)	−0.0035 (13)	−0.0012 (12)	0.0091 (10)
C13	0.0539 (14)	0.0458 (11)	0.0534 (14)	−0.0058 (11)	0.0009 (11)	0.0032 (10)
C14	0.0595 (17)	0.0515 (12)	0.0645 (16)	−0.0050 (12)	0.0059 (13)	0.0027 (11)
C15	0.113 (3)	0.0524 (13)	0.096 (2)	−0.0125 (16)	0.026 (2)	0.0189 (14)
C16	0.091 (2)	0.0784 (17)	0.096 (2)	0.0061 (17)	0.0249 (19)	0.0356 (16)
C17	0.0568 (17)	0.0571 (13)	0.0684 (16)	−0.0068 (13)	0.0037 (13)	−0.0003 (12)
C18	0.0680 (19)	0.0702 (15)	0.0794 (18)	0.0135 (16)	0.0072 (15)	−0.0077 (13)
C19	0.109 (3)	0.0585 (14)	0.0807 (19)	0.0077 (16)	−0.0041 (17)	−0.0091 (13)

Geometric parameters (Å, º) top

O1—C1	1.398 (2)	C7—H7C	0.9614
O1—C5	1.432 (2)	C8—H8A	1.0264
O2—C1	1.420 (2)	C8—H8B	1.0264
O2—C6	1.429 (2)	C8—H8C	1.0264
O3—C2	1.422 (2)	C9—C11	1.510 (3)
O3—C6	1.425 (2)	C9—C10	1.511 (4)
O4—C9	1.413 (3)	C10—H10A	1.0094
O4—C3	1.421 (2)	C10—H10B	1.0094
O5—C9	1.418 (3)	C10—H10C	1.0094
O5—C4	1.423 (3)	C11—H11A	1.0229
O6—C14	1.330 (3)	C11—H11B	1.0229
O6—C15	1.456 (2)	C11—H11C	1.0229
O7—C14	1.196 (3)	C12—C13	1.535 (3)
O8—C17	1.317 (3)	C12—H12A	1.0171
O8—C18	1.460 (3)	C12—H12B	1.0171
O9—C17	1.187 (3)	C13—C14	1.509 (3)
C1—C2	1.526 (3)	C13—C17	1.515 (3)
C1—H1A	0.9878	C13—H13A	0.9571
C2—C3	1.523 (3)	C15—C16	1.474 (4)
C2—H2A	1.0091	C15—H15A	1.0130
C3—C4	1.537 (3)	C15—H15B	1.0130
C3—H3A	1.0200	C16—H16A	0.9879
C4—C5	1.518 (3)	C16—H16B	0.9879
C4—H4A	0.9713	C16—H16C	0.9879
C5—C12	1.522 (3)	C18—C19	1.494 (3)
C5—H5A	1.0065	C18—H18A	1.0133
C6—C7	1.494 (3)	C18—H18B	1.0133
C6—C8	1.513 (3)	C19—H19A	0.9857
C7—H7A	0.9614	C19—H19B	0.9857
C7—H7B	0.9614	C19—H19C	0.9857

C1—O1—C5	113.72 (15)	O4—C9—C10	108.9 (2)
C1—O2—C6	110.56 (16)	O5—C9—C10	108.8 (2)
C2—O3—C6	106.90 (15)	C11—C9—C10	111.7 (2)
C9—O4—C3	108.33 (17)	C9—C10—H10A	109.5
C9—O5—C4	110.03 (18)	C9—C10—H10B	109.5
C14—O6—C15	117.44 (19)	H10A—C10—H10B	109.5
C17—O8—C18	116.12 (19)	C9—C10—H10C	109.5
O1—C1—O2	110.33 (18)	H10A—C10—H10C	109.5
O1—C1—C2	115.16 (18)	H10B—C10—H10C	109.5
O2—C1—C2	103.64 (15)	C9—C11—H11A	109.5
O1—C1—H1A	109.2	C9—C11—H11B	109.5
O2—C1—H1A	109.2	H11A—C11—H11B	109.5
C2—C1—H1A	109.2	C9—C11—H11C	109.5
O3—C2—C3	108.38 (19)	H11A—C11—H11C	109.5
O3—C2—C1	104.60 (18)	H11B—C11—H11C	109.5
C3—C2—C1	114.14 (18)	C5—C12—C13	112.06 (17)
O3—C2—H2A	109.8	C5—C12—H12A	109.2
C3—C2—H2A	109.8	C13—C12—H12A	109.2
C1—C2—H2A	109.8	C5—C12—H12B	109.2
O4—C3—C2	107.09 (19)	C13—C12—H12B	109.2
O4—C3—C4	104.26 (18)	H12A—C12—H12B	107.9
C2—C3—C4	114.1 (2)	C14—C13—C17	108.06 (19)
O4—C3—H3A	110.4	C14—C13—C12	112.71 (17)
C2—C3—H3A	110.4	C17—C13—C12	112.42 (17)
C4—C3—H3A	110.4	C14—C13—H13A	107.8
O5—C4—C5	109.92 (18)	C17—C13—H13A	107.8
O5—C4—C3	104.44 (18)	C12—C13—H13A	107.8
C5—C4—C3	113.11 (19)	O7—C14—O6	124.5 (2)
O5—C4—H4A	109.7	O7—C14—C13	126.2 (2)
C5—C4—H4A	109.7	O6—C14—C13	109.2 (2)
C3—C4—H4A	109.7	O6—C15—C16	107.3 (2)
O1—C5—C4	109.26 (18)	O6—C15—H15A	110.2
O1—C5—C12	107.79 (17)	C16—C15—H15A	110.2
C4—C5—C12	113.28 (17)	O6—C15—H15B	110.2
O1—C5—H5A	108.8	C16—C15—H15B	110.2
C4—C5—H5A	108.8	H15A—C15—H15B	108.5
C12—C5—H5A	108.8	C15—C16—H16A	109.5
O3—C6—O2	105.14 (15)	C15—C16—H16B	109.5
O3—C6—C7	109.3 (2)	H16A—C16—H16B	109.5
O2—C6—C7	109.6 (2)	C15—C16—H16C	109.5
O3—C6—C8	111.2 (2)	H16A—C16—H16C	109.5
O2—C6—C8	109.00 (19)	H16B—C16—H16C	109.5
C7—C6—C8	112.36 (18)	O9—C17—O8	123.5 (2)
C6—C7—H7A	109.5	O9—C17—C13	124.7 (2)
C6—C7—H7B	109.5	O8—C17—C13	111.8 (2)
H7A—C7—H7B	109.5	O8—C18—C19	108.2 (2)
C6—C7—H7C	109.5	O8—C18—H18A	110.1
H7A—C7—H7C	109.5	C19—C18—H18A	110.1
H7B—C7—H7C	109.5	O8—C18—H18B	110.1
C6—C8—H8A	109.5	C19—C18—H18B	110.1
C6—C8—H8B	109.5	H18A—C18—H18B	108.4
H8A—C8—H8B	109.5	C18—C19—H19A	109.5
C6—C8—H8C	109.5	C18—C19—H19B	109.5
H8A—C8—H8C	109.5	H19A—C19—H19B	109.5
H8B—C8—H8C	109.5	C18—C19—H19C	109.5
O4—C9—O5	106.31 (17)	H19A—C19—H19C	109.5
O4—C9—C11	111.6 (2)	H19B—C19—H19C	109.5
O5—C9—C11	109.4 (2)

C5—O1—C1—O2	78.7 (2)	C2—O3—C6—C7	−146.7 (2)
C5—O1—C1—C2	−38.2 (2)	C2—O3—C6—C8	88.7 (2)
C6—O2—C1—O1	−122.13 (19)	C1—O2—C6—O3	16.5 (3)
C6—O2—C1—C2	1.7 (3)	C1—O2—C6—C7	133.8 (2)
C6—O3—C2—C3	152.18 (19)	C1—O2—C6—C8	−102.8 (2)
C6—O3—C2—C1	30.0 (2)	C3—O4—C9—O5	−26.3 (2)
O1—C1—C2—O3	101.3 (2)	C3—O4—C9—C11	93.0 (3)
O2—C1—C2—O3	−19.2 (2)	C3—O4—C9—C10	−143.3 (2)
O1—C1—C2—C3	−16.9 (3)	C4—O5—C9—O4	17.1 (3)
O2—C1—C2—C3	−137.5 (2)	C4—O5—C9—C11	−103.5 (2)
C9—O4—C3—C2	145.74 (19)	C4—O5—C9—C10	134.2 (2)
C9—O4—C3—C4	24.4 (2)	O1—C5—C12—C13	51.9 (2)
O3—C2—C3—O4	169.21 (18)	C4—C5—C12—C13	172.91 (19)
C1—C2—C3—O4	−74.7 (3)	C5—C12—C13—C14	62.8 (2)
O3—C2—C3—C4	−76.0 (2)	C5—C12—C13—C17	−174.81 (18)
C1—C2—C3—C4	40.2 (3)	C15—O6—C14—O7	0.4 (4)
C9—O5—C4—C5	−123.7 (2)	C15—O6—C14—C13	−179.3 (2)
C9—O5—C4—C3	−2.1 (3)	C17—C13—C14—O7	−104.0 (3)
O4—C3—C4—O5	−13.5 (2)	C12—C13—C14—O7	20.9 (4)
C2—C3—C4—O5	−129.97 (19)	C17—C13—C14—O6	75.7 (3)
O4—C3—C4—C5	106.0 (2)	C12—C13—C14—O6	−159.4 (2)
C2—C3—C4—C5	−10.5 (3)	C14—O6—C15—C16	171.0 (2)
C1—O1—C5—C4	69.3 (2)	C18—O8—C17—O9	−0.5 (4)
C1—O1—C5—C12	−167.25 (15)	C18—O8—C17—C13	177.98 (19)
O5—C4—C5—O1	74.9 (2)	C14—C13—C17—O9	23.8 (3)
C3—C4—C5—O1	−41.4 (2)	C12—C13—C17—O9	−101.2 (3)
O5—C4—C5—C12	−45.3 (3)	C14—C13—C17—O8	−154.6 (2)
C3—C4—C5—C12	−161.60 (18)	C12—C13—C17—O8	80.4 (2)
C2—O3—C6—O2	−29.2 (3)	C17—O8—C18—C19	−175.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O9ⁱ	0.98	2.43	3.381 (3)	163
C5—H5A···O7	1.01	2.59	3.185 (3)	117
C8—H8B···O7ⁱ	1.03	2.56	3.577 (3)	169
C12—H12A···O5	1.02	2.42	2.811 (3)	102
C13—H13A···O1	0.96	2.43	2.814 (3)	103
C16—H16B···O1ⁱⁱ	0.99	2.51	3.422 (3)	153

Symmetry codes: (i) x−1, y, z; (ii) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₉H₃₀O₉
M_r	402.43
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	292
a, b, c (Å)	8.3287 (4), 10.8895 (4), 23.7706 (16)
V (Å³)	2155.9 (2)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.83
Crystal size (mm)	0.38 × 0.26 × 0.21

Data collection
Diffractometer	Rigaku R-AXIS RAPID II imaging plate
Absorption correction	Multi-scan (ABSCOR; Higashi,1995)
T_min, T_max	0.822, 0.840
No. of measured, independent and observed [I > 2σ(I)] reflections	9353, 3745, 2824
R_int	0.075
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.096, 1.02
No. of reflections	3745
No. of parameters	275
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.15
Absolute structure	Flack (1983), 1607 Friedel pairs
Absolute structure parameter	0.06 (18)

Computer programs: CrystalClear-SM Expert (Rigaku, 2009), HKL-2000 (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1999), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O9ⁱ	0.98	2.43	3.381 (3)	163
C5—H5A···O7	1.01	2.59	3.185 (3)	117
C8—H8B···O7ⁱ	1.03	2.56	3.577 (3)	169
C12—H12A···O5	1.02	2.42	2.811 (3)	102
C13—H13A···O1	0.96	2.43	2.814 (3)	103
C16—H16B···O1ⁱⁱ	0.99	2.51	3.422 (3)	153

Symmetry codes: (i) x−1, y, z; (ii) −x+1, y+1/2, −z+1/2.

Acknowledgements

This study was supported by the NSF (grant CHE-0922366 for X-ray diffractometer) and SUNY (grant No 1073053).

References

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Volume 66| Part 12| December 2010| Pages o3217-o3218

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

6-[Bis(ethoxycarbonyl)methyl]-6-de­oxy-1,2;3,4-di-O-iso­propyl­­idene-D-galacto­pyran­ose

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

6-[Bis(ethoxycarbonyl)methyl]-6-deoxy-1,2;3,4-di-O-isopropylidene-D-galactopyranose