1,5-Anhydro-2-de­oxy-1,2-C-dichloro­methyl­ene-3,4,6-tri-O-(4-meth­oxy­benz­yl)-d-glycero-d-gulo-hexitol

Kinfe, H.H.; Moshapo, P.T.; Muller, A.

doi:10.1107/S1600536811026870

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Pages o2012-o2013

doi:10.1107/S1600536811026870

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1,5-Anhydro-2-deoxy-1,2-C-dichloromethylene-3,4,6-tri-O-(4-methoxybenzyl)-D-glycero-D-gulo-hexitol

Henok H. Kinfe,^a ^* Paseka T. Moshapo ^a and Alfred Muller ^a ^*

^aResearch Center in Synthesis and Catalysis, Department of Chemistry, University of Johannesburg (APK Campus), PO Box 524, Auckland Park, Johannesburg 2006, South Africa
^*Correspondence e-mail: hhkinfe@uj.ac.za, mullera@uj.ac.za

(Received 10 June 2011; accepted 5 July 2011; online 13 July 2011)

The pyranosyl ring in the title compound, C₃₁H₃₄Cl₂O₇, adopts a twist-boat conformation. The 4-methoxybenzyl groups are located in equatorial positions with the methoxy groups nearly coplanar with their respective rings [dihedral angles of 0.2 (3) and 9.4 (2)°]. The aromatic rings adopt orientations enabling them to participate in C—H⋯π interactions with neighboring methoxy groups. The crystal structure is additionally stabilized by weak C—H⋯O interactions.

Related literature

For the synthesis and chemistry of cyclopropanated carbohydrates, see: Cousins & Hoberg (2000 ); Yu & Pagenkopf (2005 ). For the modified Simmons–Smith reaction route of preparing cyclopropanated sugars, see: Gammon et al. (2007 ); Ramana et al. (1997 ); Murali et al. (1995 ); Boeckman et al. (1987 ); Hoberg & Bozell (1995 ). For the dihalocarbene cyclopropanation route, see: Gammon et al. (2007); Ramana et al. (1997); Murali et al. (1995); Brimacombe et al. (1967 ); Weber & Hall (1979 ). For the diazocyclopropanation route, see: Hoberg & Claffey (1996 ); Henry & Fraser-Reid (1995 ); Timmers et al. (1996). For ring puckering analysis, see: Cremer & Pople (1975 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₃₁H₃₄Cl₂O₇
M_r = 589.48
Monoclinic, P 2₁
a = 5.3480 (4) Å
b = 18.1110 (14) Å
c = 14.8230 (11) Å
β = 91.162 (2)°
V = 1435.43 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 100 K
0.53 × 0.44 × 0.39 mm

Data collection

Bruker KappaCCD APEX DUO 4K diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.869, T_max = 0.901
13864 measured reflections
4689 independent reflections
4635 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.062
S = 1.04
4689 reflections
364 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ), 1023 Friedel pairs
Flack parameter: 0.03 (3)

Table 1
Hydrogen-bond geometry (Å, °)

Cg1, Cg2 and Cg3 are the centroids of the C17–C22, C9–C14 and C25–C30 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O1ⁱ	1.00	2.38	3.3487 (16)	164
C23—H23B⋯O7ⁱⁱ	0.98	2.50	3.399 (2)	153
C26—H26⋯O3ⁱ	0.95	2.54	3.2301 (16)	130
C31—H31C⋯O1ⁱⁱⁱ	0.98	2.49	3.466 (2)	172
C15—H15A⋯Cg1^iv	0.98	2.95	3.927 (3)	174
C15—H15C⋯Cg2^v	0.98	2.99	3.873 (2)	151
C24—H24B⋯Cg3^v	0.99	2.90	3.7983 (17)	152
Symmetry codes: (i) x-1, y, z; (ii) x+1, y, z+1; (iii) $[-x, y+{\script{1\over 2}}, -z]$ ; (iv) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (v) x+1, y, z.

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus and XPREP (Bruker, 2007); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811026870/mw2012sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811026870/mw2012Isup2.hkl

checkCIF report

Comment top

1,2-Cyclopropanated sugars have found widespread applications in organic synthesis (Cousins & Hoberg, 2000; Yu & Pagenkopf, 2005). The high reactivity of strained cyclopropanes in conjunction with the inherent optical purity of sugars makes cyclopropanated carbohydrates indispensable chiral building blocks. Due to the resemblance of cyclopropyl to an olefinic functionality and assistance from the lone pair of electrons on the pyran ring oxygen atom, 1,2-cyclopropanated sugars undergo regioselective ring opening to afford 2-C branched and C-1 functionalized sugar derivatives (Gammon et al., 2007; Ramana et al., 1997; Murali et al., 1995). The most common methods of preparing cyclopropanated sugars are: the modified Simmons-Smith reaction (see Gammon et al., 2007; Ramana et al., 1997; Murali et al., 1995; Boeckman et al., 1987; Hoberg & Bozell, 1995), dihalocarbene cyclopropanation (see Gammon et al., 2007; Ramana et al., 1997; Murali et al., 1995; Brimacombe et al., 1967; Weber & Hall, 1979) and diazocyclopropanation (see Hoberg & Claffey, 1996; Henry & Fraser-Reid, 1995; Timmers et al., 1996). The Simmons-Smith cyclopropanation involves treating a glycal with CH₂I₂/Zn/CuCl activated with acetyl chloride. Under those conditions a cyclopropane syn to the oxygen of the C-3 of the respective glycal is formed. On the other hand, the dihalocarbene cyclopropanation of glycals affords a cyclopropane with a stereochemistry opposite to that of the Simmons-Smith cyclopropanation. Herein we report the dihalocarbene cyclopropanation of per-p-methoxybenzyl protected glucal (A in Fig. 2) and the confirmation of the stereochemistry of the cyclopropanated product (I in Fig. 2).

The title compound (see Fig. 1 and Scheme 1) crystallizes in the P2₁ (Z=2) space group resulting in molecules lying on general positions in the unit cell. All bond lengths are within their normal ranges (Allen et al., 1987). The pyran ring is in a twist-boat conformation with ring puckering parameters of q₂ = 0.7035 (14) Å, q₃ = -0.0851 (15) Å, Q = 0.7086 (14)Å and ϕ₂ = 346.57 (12)° (see Cremer & Pople, 1975). The O-p-methoxybenzyl groups are all in equatorial positions with the methoxy groups nearly coplanar with their respective rings (dihedral angles of 0.16 (27)° and 9.36 (21)° for rings C9—C14 and C17—C22 respectively). The aromatic rings adopt orientations enabling them to participate in C—H···Cg interactions with neighboring methoxy groups (Table 1). There are also several weak C—H···O interactions (Table 1) that aid in the stabilization of the crystal structure.

Related literature top

For the synthesis and chemistry of cyclopropanated carbohydrates, see: Cousins & Hoberg (2000); Yu & Pagenkopf (2005). For the modified Simmons–Smith reaction route of preparing cyclopropanated sugars, see: Gammon et al. (2007); Ramana et al. (1997); Murali et al. (1995); Boeckman et al. (1987); Hoberg & Bozell (1995). For the dihalocarbene cyclopropanation route, see: Gammon et al. (2007); Ramana et al. (1997); Murali et al. (1995); Brimacombe et al. (1967); Weber & Hall (1979). For the diazocyclopropanation route, see: Hoberg & Claffey (1996); Henry & Fraser-Reid (1995); Timmers et al. (1996). For ring puckering analysis, see: Cremer & Pople (1975). For standard bond lengths, see: Allen et al. (1987).

Experimental top

50% aq NaOH (3 mL) was added to a vigorously stirred solution of glucal (see A in Fig. 2; 0.5 g, 0.99 mmol) in chloroform (5 ml) containing benzyltriethylammonium chloride (0.11 g, 0.49 mmol). After stirring at 35°C overnight, the reaction mixture was diluted with water and the aqueous phase was extracted with dichloromethane. The combined organic phases were dried over MgSO₄, filtered and evaporated in vacuo. Chromatography on silica gel (ethyl acetate/hexane, 5:95) of the residue and recrystallization from hexane gave the title compound in 80% yield as a white solid.

Analytical data: ¹H NMR (CDCl₃, 400 MHz) δ 7.32 (d, J = 8.0 Hz, 2H), 7.21 (d, J = 8.4 Hz, 2H), 7.11 (d, J = 8.0 Hz, 2H), 6.88 (d, J = 8.4 Hz, 2H), 6.86 (d, J = 8.0 Hz, 2H), 6.81 (d, J = 8.0 Hz, 2H), 4.77 (d, J = 10.8 Hz, 2H), 4.70 (d, J = 11.2 Hz, 2H), 4.60 (d, J = 11.2 Hz, 2H), 4.46 (d, J = 12.4 Hz, 2H), 4.42 (d, J = 12.4 Hz, 2H), 4.35 (d, J = 11.6 Hz, 2H), 3.84 (d, J = 8.0 Hz, 1H), 3.82–3.60 (m, 12H), 3.58–3.40 (m, 2H), 1.73 (dd, J = 4.2 and 7.8 Hz, 1H); ¹³C NMR (CDCl₃, 100 MHz) δ 159.4, 159.3, 159.2, 130.4, 130.0, 129.8, 129.7, 129.5, 129.3, 113.9, 113.8, 113.7, 79.8, 74.7, 74.1, 72.9, 71.5, 69.7, 61.5, 58.9, 55.2, 34.3.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus and XPREP (Bruker, 2007); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. View of I. Displacement ellipsoids are drawn at a 50% probability level. Hydrogen atoms are omitted for clarity.
	Fig. 2. Reaction scheme for the dihalocarbene cyclopropanation of the protected glucal (PMB = p-methoxybenzyl).

1,5-Anhydro-2-deoxy-1,2-C-dichloromethylene-3,4,6-tri-O-(4-methoxybenzyl)-D-glycero-D-gulo-hexitol top

Crystal data top

C₃₁H₃₄Cl₂O₇	F(000) = 620
M_r = 589.48	D_x = 1.364 Mg m⁻³
Monoclinic, P2₁	Melting point = 343–345 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 5.3480 (4) Å	Cell parameters from 9926 reflections
b = 18.1110 (14) Å	θ = 2.6–28.3°
c = 14.8230 (11) Å	µ = 0.27 mm⁻¹
β = 91.162 (2)°	T = 100 K
V = 1435.43 (19) Å³	Cuboid, colourless
Z = 2	0.53 × 0.44 × 0.39 mm

Data collection top

Bruker KappaCCD APEX DUO 4K diffractometer	4635 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 28.3°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2007)\bbr00	h = −7→7
T_min = 0.869, T_max = 0.901	k = −11→24
13864 measured reflections	l = −19→19
4689 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.023	H-atom parameters constrained
wR(F²) = 0.062	w = 1/[σ²(F_o²) + (0.0333P)² + 0.3097P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
4689 reflections	Δρ_max = 0.28 e Å⁻³
364 parameters	Δρ_min = −0.16 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1023 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (3)

Crystal data top

C₃₁H₃₄Cl₂O₇	V = 1435.43 (19) Å³
M_r = 589.48	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 5.3480 (4) Å	µ = 0.27 mm⁻¹
b = 18.1110 (14) Å	T = 100 K
c = 14.8230 (11) Å	0.53 × 0.44 × 0.39 mm
β = 91.162 (2)°

Data collection top

Bruker KappaCCD APEX DUO 4K diffractometer	4689 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)\bbr00	4635 reflections with I > 2σ(I)
T_min = 0.869, T_max = 0.901	R_int = 0.026
13864 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	H-atom parameters constrained
wR(F²) = 0.062	Δρ_max = 0.28 e Å⁻³
S = 1.04	Δρ_min = −0.16 e Å⁻³
4689 reflections	Absolute structure: Flack (1983), 1023 Friedel pairs
364 parameters	Absolute structure parameter: 0.03 (3)
1 restraint

Special details top

Experimental. The intensity data was collected on a Bruker APEX Duo 4 K KappaCCD diffractometer using an exposure time of 60 s/frame. A total of 1324 frames were collected with a frame width of 0.5° covering up to θ = 28.3° with 99.6% completeness accomplished.

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
C1	0.5746 (3)	0.37183 (8)	0.12955 (9)	0.0159 (3)
H1	0.7267	0.4023	0.1182	0.019*
C2	0.3481 (3)	0.41817 (8)	0.09697 (9)	0.0141 (3)
H2	0.2059	0.4114	0.139	0.017*
C3	0.2681 (2)	0.39508 (8)	0.00162 (9)	0.0135 (2)
H3	0.4112	0.401	−0.0402	0.016*
C4	0.1924 (2)	0.31426 (8)	0.00670 (9)	0.0143 (2)
H4	0.0124	0.3039	0.0186	0.017*
C5	0.3834 (2)	0.26695 (8)	0.05720 (9)	0.0162 (3)
H5	0.3203	0.2289	0.1001	0.019*
C6	0.3340 (3)	0.25520 (8)	−0.04201 (9)	0.0160 (3)
C7	0.5711 (3)	0.35798 (9)	0.23087 (9)	0.0203 (3)
H7A	0.7335	0.3372	0.2517	0.024*
H7B	0.5436	0.405	0.2632	0.024*
C8	0.2633 (3)	0.31871 (11)	0.33538 (10)	0.0256 (3)
H8A	0.1314	0.2811	0.3435	0.031*
H8B	0.1815	0.3677	0.3354	0.031*
C9	0.4444 (3)	0.31468 (10)	0.41480 (9)	0.0225 (3)
C10	0.6119 (3)	0.25666 (10)	0.42635 (10)	0.0252 (3)
H10	0.6156	0.2183	0.3826	0.03*
C11	0.7754 (3)	0.25366 (10)	0.50125 (10)	0.0263 (3)
H11	0.8919	0.2143	0.5075	0.032*
C12	0.7657 (3)	0.30875 (11)	0.56633 (11)	0.0286 (3)
C13	0.5962 (4)	0.36662 (12)	0.55592 (13)	0.0366 (4)
H13	0.5882	0.4041	0.6006	0.044*
C14	0.4393 (4)	0.36961 (11)	0.48059 (12)	0.0315 (4)
H14	0.3263	0.4098	0.4736	0.038*
C15	1.0910 (4)	0.25312 (14)	0.65659 (15)	0.0446 (5)
H15A	1.0016	0.2063	0.6636	0.067*
H15B	1.1919	0.263	0.7112	0.067*
H15C	1.2005	0.25	0.6045	0.067*
C16	0.2468 (3)	0.54661 (9)	0.12345 (9)	0.0173 (3)
H16A	0.0832	0.5318	0.0967	0.021*
H16B	0.2925	0.5951	0.0978	0.021*
C17	0.2251 (3)	0.55341 (8)	0.22438 (9)	0.0167 (3)
C18	0.0275 (3)	0.52223 (9)	0.27015 (10)	0.0207 (3)
H18	−0.1031	0.4985	0.2368	0.025*
C19	0.0161 (3)	0.52497 (10)	0.36452 (10)	0.0228 (3)
H19	−0.12	0.5032	0.395	0.027*
C20	0.2065 (3)	0.55998 (9)	0.41261 (10)	0.0206 (3)
C21	0.4042 (3)	0.59335 (10)	0.36741 (10)	0.0229 (3)
H21	0.5321	0.6185	0.4006	0.027*
C22	0.4127 (3)	0.58960 (9)	0.27443 (10)	0.0206 (3)
H22	0.5479	0.6119	0.244	0.025*
C23	0.0028 (4)	0.54396 (14)	0.55311 (11)	0.0376 (5)
H23A	−0.145	0.5696	0.5286	0.056*
H23B	0.0258	0.5565	0.6171	0.056*
H23C	−0.0205	0.4905	0.5469	0.056*
C24	0.0170 (3)	0.43201 (9)	−0.12203 (9)	0.0156 (3)
H24A	−0.0304	0.3803	−0.1355	0.019*
H24B	0.1702	0.4437	−0.1556	0.019*
C25	−0.1908 (3)	0.48286 (8)	−0.15179 (8)	0.0149 (3)
C26	−0.3255 (3)	0.52635 (9)	−0.09302 (9)	0.0157 (3)
H26	−0.2869	0.5243	−0.0302	0.019*
C27	−0.5166 (3)	0.57303 (9)	−0.12405 (9)	0.0165 (3)
H27	−0.608	0.6019	−0.0826	0.02*
C28	−0.5722 (3)	0.57693 (9)	−0.21629 (9)	0.0174 (3)
C29	−0.4381 (3)	0.53311 (10)	−0.27614 (9)	0.0223 (3)
H29	−0.4757	0.5352	−0.339	0.027*
C30	−0.2511 (3)	0.48674 (9)	−0.24411 (9)	0.0202 (3)
H30	−0.1619	0.457	−0.2854	0.024*
C31	−0.9079 (3)	0.66226 (9)	−0.19589 (10)	0.0229 (3)
H31A	−0.9814	0.6293	−0.1512	0.034*
H31B	−1.0416	0.6865	−0.231	0.034*
H31C	−0.8057	0.6998	−0.1649	0.034*
O1	0.60536 (18)	0.30368 (6)	0.08006 (7)	0.0172 (2)
O2	0.3745 (2)	0.30744 (7)	0.24945 (7)	0.0234 (2)
O3	0.43372 (19)	0.49265 (6)	0.10078 (7)	0.0165 (2)
O4	0.06550 (18)	0.44011 (6)	−0.02738 (6)	0.0157 (2)
O5	0.9144 (3)	0.31154 (10)	0.64279 (9)	0.0426 (4)
O6	0.2183 (2)	0.56619 (8)	0.50476 (7)	0.0269 (3)
O7	−0.7547 (2)	0.62045 (7)	−0.25488 (7)	0.0228 (2)
Cl1	0.55865 (6)	0.27721 (2)	−0.12181 (2)	0.02147 (8)
Cl2	0.16666 (7)	0.17496 (2)	−0.07142 (3)	0.02262 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0144 (6)	0.0158 (7)	0.0173 (6)	0.0011 (5)	−0.0020 (5)	−0.0001 (5)
C2	0.0148 (6)	0.0141 (7)	0.0136 (5)	−0.0005 (5)	0.0001 (4)	0.0008 (5)
C3	0.0134 (6)	0.0132 (6)	0.0138 (5)	0.0018 (5)	−0.0003 (4)	0.0003 (5)
C4	0.0131 (6)	0.0128 (6)	0.0170 (5)	−0.0003 (5)	−0.0001 (4)	0.0000 (5)
C5	0.0153 (6)	0.0140 (7)	0.0192 (6)	0.0003 (5)	−0.0019 (5)	0.0014 (5)
C6	0.0135 (6)	0.0146 (7)	0.0198 (6)	−0.0024 (5)	−0.0001 (5)	−0.0021 (5)
C7	0.0213 (7)	0.0225 (8)	0.0170 (6)	−0.0019 (6)	−0.0056 (5)	0.0017 (6)
C8	0.0262 (7)	0.0330 (9)	0.0175 (6)	−0.0021 (7)	−0.0026 (5)	0.0029 (6)
C9	0.0256 (7)	0.0240 (8)	0.0177 (6)	−0.0037 (6)	−0.0018 (5)	0.0032 (6)
C10	0.0315 (8)	0.0255 (9)	0.0186 (6)	−0.0003 (7)	−0.0004 (6)	−0.0021 (6)
C11	0.0296 (8)	0.0246 (8)	0.0244 (7)	0.0027 (7)	−0.0017 (6)	0.0036 (6)
C12	0.0313 (8)	0.0304 (9)	0.0238 (7)	−0.0019 (7)	−0.0094 (6)	0.0003 (7)
C13	0.0479 (11)	0.0282 (10)	0.0332 (9)	0.0030 (9)	−0.0153 (8)	−0.0117 (8)
C14	0.0377 (9)	0.0235 (9)	0.0329 (8)	0.0042 (7)	−0.0107 (7)	−0.0032 (7)
C15	0.0461 (11)	0.0433 (12)	0.0434 (10)	0.0023 (10)	−0.0240 (9)	0.0071 (9)
C16	0.0207 (6)	0.0159 (7)	0.0154 (6)	0.0036 (6)	−0.0008 (5)	−0.0011 (5)
C17	0.0185 (6)	0.0156 (7)	0.0160 (6)	0.0042 (6)	−0.0008 (5)	−0.0022 (5)
C18	0.0200 (6)	0.0222 (8)	0.0198 (6)	−0.0007 (6)	0.0000 (5)	−0.0044 (6)
C19	0.0225 (7)	0.0252 (8)	0.0210 (6)	−0.0023 (6)	0.0051 (5)	−0.0024 (6)
C20	0.0226 (7)	0.0228 (8)	0.0164 (6)	0.0038 (6)	0.0000 (5)	−0.0013 (6)
C21	0.0209 (7)	0.0283 (9)	0.0193 (6)	−0.0014 (6)	−0.0033 (5)	−0.0036 (6)
C22	0.0193 (7)	0.0232 (8)	0.0194 (6)	−0.0020 (6)	0.0014 (5)	−0.0017 (6)
C23	0.0373 (9)	0.0563 (14)	0.0193 (7)	−0.0073 (10)	0.0069 (7)	−0.0003 (8)
C24	0.0193 (6)	0.0150 (7)	0.0124 (5)	0.0003 (5)	−0.0012 (4)	−0.0006 (5)
C25	0.0164 (6)	0.0144 (6)	0.0140 (5)	−0.0032 (5)	−0.0007 (5)	0.0012 (5)
C26	0.0186 (6)	0.0159 (7)	0.0125 (5)	−0.0029 (5)	−0.0008 (5)	0.0014 (5)
C27	0.0185 (6)	0.0151 (7)	0.0160 (6)	−0.0022 (5)	0.0016 (5)	−0.0004 (5)
C28	0.0171 (6)	0.0177 (7)	0.0173 (6)	−0.0008 (5)	−0.0005 (5)	0.0028 (5)
C29	0.0247 (7)	0.0285 (9)	0.0134 (5)	0.0037 (7)	−0.0020 (5)	−0.0002 (6)
C30	0.0238 (7)	0.0234 (8)	0.0134 (6)	0.0036 (6)	−0.0005 (5)	−0.0025 (6)
C31	0.0211 (7)	0.0199 (8)	0.0277 (7)	0.0014 (6)	−0.0016 (6)	−0.0004 (6)
O1	0.0137 (4)	0.0163 (5)	0.0215 (4)	0.0012 (4)	−0.0024 (3)	−0.0021 (4)
O2	0.0285 (5)	0.0264 (6)	0.0151 (4)	−0.0079 (5)	−0.0027 (4)	0.0027 (4)
O3	0.0182 (5)	0.0140 (5)	0.0176 (4)	−0.0005 (4)	0.0023 (4)	−0.0028 (4)
O4	0.0185 (5)	0.0161 (5)	0.0123 (4)	0.0046 (4)	−0.0021 (3)	0.0003 (4)
O5	0.0490 (8)	0.0447 (9)	0.0331 (6)	0.0073 (7)	−0.0226 (6)	−0.0062 (6)
O6	0.0290 (6)	0.0368 (7)	0.0149 (5)	−0.0019 (5)	0.0007 (4)	−0.0011 (5)
O7	0.0223 (5)	0.0268 (6)	0.0192 (5)	0.0066 (5)	−0.0027 (4)	0.0030 (4)
Cl1	0.01893 (15)	0.02378 (18)	0.02188 (15)	−0.00135 (14)	0.00472 (12)	−0.00492 (14)
Cl2	0.02241 (16)	0.01435 (16)	0.03092 (17)	−0.00321 (14)	−0.00394 (13)	−0.00353 (14)

Geometric parameters (Å, º) top

C1—O1	1.4469 (18)	C15—H15C	0.98
C1—C7	1.5231 (18)	C16—O3	1.4425 (17)
C1—C2	1.5433 (19)	C16—C17	1.5080 (18)
C1—H1	1	C16—H16A	0.99
C2—O3	1.4252 (18)	C16—H16B	0.99
C2—C3	1.5267 (18)	C17—C18	1.388 (2)
C2—H2	1	C17—C22	1.399 (2)
C3—O4	1.4159 (16)	C18—C19	1.402 (2)
C3—C4	1.521 (2)	C18—H18	0.95
C3—H3	1	C19—C20	1.385 (2)
C4—C6	1.504 (2)	C19—H19	0.95
C4—C5	1.5189 (19)	C20—O6	1.3707 (17)
C4—H4	1	C20—C21	1.400 (2)
C5—O1	1.3966 (17)	C21—C22	1.382 (2)
C5—C6	1.5039 (19)	C21—H21	0.95
C5—H5	1	C22—H22	0.95
C6—Cl1	1.7489 (14)	C23—O6	1.427 (2)
C6—Cl2	1.7570 (15)	C23—H23A	0.98
C7—O2	1.4252 (19)	C23—H23B	0.98
C7—H7A	0.99	C23—H23C	0.98
C7—H7B	0.99	C24—O4	1.4292 (15)
C8—O2	1.4312 (18)	C24—C25	1.503 (2)
C8—C9	1.511 (2)	C24—H24A	0.99
C8—H8A	0.99	C24—H24B	0.99
C8—H8B	0.99	C25—C26	1.3869 (19)
C9—C10	1.389 (2)	C25—C30	1.4013 (18)
C9—C14	1.394 (2)	C26—C27	1.397 (2)
C10—C11	1.400 (2)	C26—H26	0.95
C10—H10	0.95	C27—C28	1.3951 (18)
C11—C12	1.389 (2)	C27—H27	0.95
C11—H11	0.95	C28—O7	1.3705 (18)
C12—O5	1.3724 (19)	C28—C29	1.399 (2)
C12—C13	1.392 (3)	C29—C30	1.383 (2)
C13—C14	1.384 (2)	C29—H29	0.95
C13—H13	0.95	C30—H30	0.95
C14—H14	0.95	C31—O7	1.4277 (18)
C15—O5	1.430 (3)	C31—H31A	0.98
C15—H15A	0.98	C31—H31B	0.98
C15—H15B	0.98	C31—H31C	0.98

O1—C1—C7	111.30 (12)	H15A—C15—H15C	109.5
O1—C1—C2	113.69 (11)	H15B—C15—H15C	109.5
C7—C1—C2	111.89 (11)	O3—C16—C17	110.74 (11)
O1—C1—H1	106.5	O3—C16—H16A	109.5
C7—C1—H1	106.5	C17—C16—H16A	109.5
C2—C1—H1	106.5	O3—C16—H16B	109.5
O3—C2—C3	112.32 (11)	C17—C16—H16B	109.5
O3—C2—C1	104.64 (11)	H16A—C16—H16B	108.1
C3—C2—C1	110.13 (11)	C18—C17—C22	118.47 (13)
O3—C2—H2	109.9	C18—C17—C16	121.78 (13)
C3—C2—H2	109.9	C22—C17—C16	119.71 (13)
C1—C2—H2	109.9	C17—C18—C19	121.48 (14)
O4—C3—C4	111.51 (11)	C17—C18—H18	119.3
O4—C3—C2	108.76 (11)	C19—C18—H18	119.3
C4—C3—C2	106.72 (11)	C20—C19—C18	118.90 (14)
O4—C3—H3	109.9	C20—C19—H19	120.5
C4—C3—H3	109.9	C18—C19—H19	120.5
C2—C3—H3	109.9	O6—C20—C19	124.68 (14)
C6—C4—C5	59.67 (9)	O6—C20—C21	114.93 (13)
C6—C4—C3	121.57 (11)	C19—C20—C21	120.39 (13)
C5—C4—C3	112.98 (11)	C22—C21—C20	119.77 (14)
C6—C4—H4	116.6	C22—C21—H21	120.1
C5—C4—H4	116.6	C20—C21—H21	120.1
C3—C4—H4	116.6	C21—C22—C17	120.96 (14)
O1—C5—C6	115.86 (11)	C21—C22—H22	119.5
O1—C5—C4	114.25 (12)	C17—C22—H22	119.5
C6—C5—C4	59.67 (9)	O6—C23—H23A	109.5
O1—C5—H5	118	O6—C23—H23B	109.5
C6—C5—H5	118	H23A—C23—H23B	109.5
C4—C5—H5	118	O6—C23—H23C	109.5
C5—C6—C4	60.66 (9)	H23A—C23—H23C	109.5
C5—C6—Cl1	121.32 (10)	H23B—C23—H23C	109.5
C4—C6—Cl1	121.48 (11)	O4—C24—C25	110.10 (11)
C5—C6—Cl2	115.98 (10)	O4—C24—H24A	109.6
C4—C6—Cl2	116.64 (10)	C25—C24—H24A	109.6
Cl1—C6—Cl2	111.97 (8)	O4—C24—H24B	109.6
O2—C7—C1	108.68 (11)	C25—C24—H24B	109.6
O2—C7—H7A	110	H24A—C24—H24B	108.2
C1—C7—H7A	110	C26—C25—C30	118.22 (13)
O2—C7—H7B	110	C26—C25—C24	123.65 (12)
C1—C7—H7B	110	C30—C25—C24	118.13 (12)
H7A—C7—H7B	108.3	C25—C26—C27	121.51 (12)
O2—C8—C9	114.52 (13)	C25—C26—H26	119.2
O2—C8—H8A	108.6	C27—C26—H26	119.2
C9—C8—H8A	108.6	C28—C27—C26	119.56 (13)
O2—C8—H8B	108.6	C28—C27—H27	120.2
C9—C8—H8B	108.6	C26—C27—H27	120.2
H8A—C8—H8B	107.6	O7—C28—C27	125.03 (13)
C10—C9—C14	118.39 (15)	O7—C28—C29	115.55 (12)
C10—C9—C8	122.28 (15)	C27—C28—C29	119.41 (14)
C14—C9—C8	119.29 (16)	C30—C29—C28	120.22 (13)
C9—C10—C11	121.18 (16)	C30—C29—H29	119.9
C9—C10—H10	119.4	C28—C29—H29	119.9
C11—C10—H10	119.4	C29—C30—C25	121.08 (13)
C12—C11—C10	119.42 (16)	C29—C30—H30	119.5
C12—C11—H11	120.3	C25—C30—H30	119.5
C10—C11—H11	120.3	O7—C31—H31A	109.5
O5—C12—C11	124.79 (17)	O7—C31—H31B	109.5
O5—C12—C13	115.41 (16)	H31A—C31—H31B	109.5
C11—C12—C13	119.80 (15)	O7—C31—H31C	109.5
C14—C13—C12	120.10 (17)	H31A—C31—H31C	109.5
C14—C13—H13	119.9	H31B—C31—H31C	109.5
C12—C13—H13	119.9	C5—O1—C1	115.13 (10)
C13—C14—C9	121.09 (17)	C7—O2—C8	113.70 (12)
C13—C14—H14	119.5	C2—O3—C16	115.26 (10)
C9—C14—H14	119.5	C3—O4—C24	111.19 (10)
O5—C15—H15A	109.5	C12—O5—C15	117.45 (16)
O5—C15—H15B	109.5	C20—O6—C23	117.13 (13)
H15A—C15—H15B	109.5	C28—O7—C31	117.52 (11)
O5—C15—H15C	109.5

O1—C1—C2—O3	−140.75 (11)	C22—C17—C18—C19	−1.4 (2)
C7—C1—C2—O3	92.10 (13)	C16—C17—C18—C19	176.15 (15)
O1—C1—C2—C3	−19.84 (16)	C17—C18—C19—C20	0.3 (3)
C7—C1—C2—C3	−146.98 (12)	C18—C19—C20—O6	−179.70 (15)
O3—C2—C3—O4	−61.95 (14)	C18—C19—C20—C21	1.3 (3)
C1—C2—C3—O4	−178.14 (11)	O6—C20—C21—C22	179.18 (15)
O3—C2—C3—C4	177.64 (10)	C19—C20—C21—C22	−1.7 (3)
C1—C2—C3—C4	61.44 (13)	C20—C21—C22—C17	0.6 (3)
O4—C3—C4—C6	125.64 (12)	C18—C17—C22—C21	1.0 (2)
C2—C3—C4—C6	−115.73 (13)	C16—C17—C22—C21	−176.63 (15)
O4—C3—C4—C5	−166.90 (10)	O4—C24—C25—C26	−4.7 (2)
C2—C3—C4—C5	−48.27 (14)	O4—C24—C25—C30	175.07 (13)
C6—C4—C5—O1	106.90 (13)	C30—C25—C26—C27	0.0 (2)
C3—C4—C5—O1	−7.35 (15)	C24—C25—C26—C27	179.74 (14)
C3—C4—C5—C6	−114.25 (12)	C25—C26—C27—C28	−0.8 (2)
O1—C5—C6—C4	−104.19 (14)	C26—C27—C28—O7	179.99 (14)
O1—C5—C6—Cl1	6.86 (18)	C26—C27—C28—C29	1.0 (2)
C4—C5—C6—Cl1	111.05 (13)	O7—C28—C29—C30	−179.52 (15)
O1—C5—C6—Cl2	148.46 (10)	C27—C28—C29—C30	−0.4 (2)
C4—C5—C6—Cl2	−107.35 (11)	C28—C29—C30—C25	−0.4 (3)
C3—C4—C6—C5	99.86 (14)	C26—C25—C30—C29	0.6 (2)
C5—C4—C6—Cl1	−110.80 (12)	C24—C25—C30—C29	−179.18 (15)
C3—C4—C6—Cl1	−10.94 (18)	C6—C5—O1—C1	120.36 (13)
C5—C4—C6—Cl2	106.27 (12)	C4—C5—O1—C1	53.75 (15)
C3—C4—C6—Cl2	−153.86 (10)	C7—C1—O1—C5	88.59 (14)
O1—C1—C7—O2	−57.49 (15)	C2—C1—O1—C5	−38.87 (15)
C2—C1—C7—O2	70.93 (16)	C1—C7—O2—C8	−148.42 (13)
O2—C8—C9—C10	−49.6 (2)	C9—C8—O2—C7	−57.37 (19)
O2—C8—C9—C14	132.47 (17)	C3—C2—O3—C16	93.89 (13)
C14—C9—C10—C11	−1.1 (2)	C1—C2—O3—C16	−146.66 (10)
C8—C9—C10—C11	−179.03 (15)	C17—C16—O3—C2	85.55 (14)
C9—C10—C11—C12	1.6 (3)	C4—C3—O4—C24	−74.90 (13)
C10—C11—C12—O5	179.50 (17)	C2—C3—O4—C24	167.69 (11)
C10—C11—C12—C13	−0.7 (3)	C25—C24—O4—C3	−177.44 (11)
O5—C12—C13—C14	179.22 (19)	C11—C12—O5—C15	−0.4 (3)
C11—C12—C13—C14	−0.6 (3)	C13—C12—O5—C15	179.80 (19)
C12—C13—C14—C9	1.1 (3)	C19—C20—O6—C23	−9.0 (3)
C10—C9—C14—C13	−0.2 (3)	C21—C20—O6—C23	170.06 (17)
C8—C9—C14—C13	177.76 (18)	C27—C28—O7—C31	−3.3 (2)
O3—C16—C17—C18	−103.82 (16)	C29—C28—O7—C31	175.76 (14)
O3—C16—C17—C22	73.73 (18)

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2 and Cg3 are the centroids of the C17–C22, C9–C14 and C25–C30 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1ⁱ	1.00	2.38	3.3487 (16)	164
C23—H23B···O7ⁱⁱ	0.98	2.50	3.399 (2)	153
C26—H26···O3ⁱ	0.95	2.54	3.2301 (16)	130
C31—H31C···O1ⁱⁱⁱ	0.98	2.49	3.466 (2)	172
C15—H15A···Cg1^iv	0.98	2.95	3.927 (3)	174
C15—H15C···Cg2^v	0.98	2.99	3.873 (2)	151
C24—H24B···Cg3^v	0.99	2.90	3.7983 (17)	152

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

Experimental details

Crystal data
Chemical formula	C₃₁H₃₄Cl₂O₇
M_r	589.48
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	5.3480 (4), 18.1110 (14), 14.8230 (11)
β (°)	91.162 (2)
V (Å³)	1435.43 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.53 × 0.44 × 0.39

Data collection
Diffractometer	Bruker KappaCCD APEX DUO 4K diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)\bbr00
T_min, T_max	0.869, 0.901
No. of measured, independent and observed [I > 2σ(I)] reflections	13864, 4689, 4635
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.062, 1.04
No. of reflections	4689
No. of parameters	364
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.16
Absolute structure	Flack (1983), 1023 Friedel pairs
Absolute structure parameter	0.03 (3)

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SAINT-Plus and XPREP (Bruker, 2007), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2 and Cg3 are the centroids of the C17–C22, C9–C14 and C25–C30 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1ⁱ	1.00	2.38	3.3487 (16)	164
C23—H23B···O7ⁱⁱ	0.98	2.50	3.399 (2)	153
C26—H26···O3ⁱ	0.95	2.54	3.2301 (16)	130
C31—H31C···O1ⁱⁱⁱ	0.98	2.49	3.466 (2)	172
C15—H15A···Cg1^iv	0.98	2.95	3.927 (3)	174
C15—H15C···Cg2^v	0.98	2.99	3.873 (2)	151
C24—H24B···Cg3^v	0.99	2.90	3.7983 (17)	152

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

Acknowledgements

Research funds of the University of Johannesburg and the Center for Synthesis and Catalysis are gratefully acknowledged. Mr C. Ncube is thanked for the data collection.

References

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

1,5-Anhydro-2-de­­oxy-1,2-C-di­chloro­methyl­ene-3,4,6-tri-O-(4-meth­­oxy­benz­yl)-D-glycero-D-gulo-hexitol

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

1,5-Anhydro-2-deoxy-1,2-C-dichloromethylene-3,4,6-tri-O-(4-methoxybenzyl)-D-glycero-D-gulo-hexitol