1,5-Anhydro-3,6-di-O-benzyl-2-de­oxy-1,2-C-dichloro­methyl­ene-d-glycero-d-gulo-hexitol

Kinfe, H.H.; Aderibigbe, B.A.; Muller, A.

doi:10.1107/S1600536811040815

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2888

doi:10.1107/S1600536811040815

Open

access

1,5-Anhydro-3,6-di-O-benzyl-2-deoxy-1,2-C-dichloromethylene-D-glycero-D-gulo-hexitol

Henok H. Kinfe,^a ^* Blessing A. Aderibigbe ^a and Alfred Muller ^a ^*

^aResearch Center for 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 26 September 2011; accepted 4 October 2011; online 8 October 2011)

In the title compound, C₂₁H₂₂Cl₂O₄, the pyranosyl ring adopts a twist-boat conformation with the O-benzyl groups in equatorial positions. In the crystal, O—H⋯O hydrogen bonding results in infinite chains of molecules along [100]. The structure is further consolidated by weak C—H⋯O, C—H⋯Cl and C—H⋯π interactions. The absolute structure was determined.

Related literature

For O-benzyl deprotection methodologies, see: Akiyama et al. (1991 ). For a related structure, see: Shanmugasundaram et al. (2002 ). For ring puckering analysis, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₂₁H₂₂Cl₂O₄
M_r = 409.29
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.2985 (1) Å
b = 18.8511 (3) Å
c = 19.5973 (4) Å
V = 1957.43 (6) Å³
Z = 4
Cu Kα radiation
μ = 3.19 mm⁻¹
T = 100 K
0.16 × 0.06 × 0.05 mm

Data collection

Bruker APEX DUO 4K CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.630, T_max = 0.857
14434 measured reflections
3241 independent reflections
3108 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.055
S = 1.05
3241 reflections
245 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.19 e Å⁻³
Absolute structure: Flack (1983 ), 1327 Friedel Pairs
Flack parameter: 0.009 (9)

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C1–C7 and C17–C22 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O3ⁱ	0.84	2.18	2.9905 (10)	163
C13—H13⋯O2ⁱⁱ	1.00	2.45	3.4005 (19)	158
C18—H18⋯O3ⁱ	0.95	2.58	3.521 (2)	171
C20—H20⋯Cl1ⁱⁱⁱ	0.95	2.75	3.6268 (19)	154
C8—H8B⋯Cg1^iv	0.99	2.76	3.7480 (18)	175
C16—H16B⋯Cg2^iv	0.99	2.79	3.7195 (17)	156
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+2]$ ; (ii) x+1, y, z; (iii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) x-1, y, z.

Data collection: APEX2 (Bruker, 2011 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); 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/S1600536811040815/pv2453sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811040815/pv2453Isup2.hkl

checkCIF report

Comment top

A combination of AlCl₃ and a base additive such as N,N-dimethylaniline cleaves benzyl ethers efficiently (Akiyama et al., 1991). We have found that treatment of dichlorocyclopropyl sugar derivative A with AlCl₃ in toluene and in the absence of a base additive resulted to selective deprotection and afforded 4-O-debenzylated sugar derivative I in 73% yield (Fig. 2). Although ¹H NMR data could be used to establish the structure of the product, the highly reactive and strained bicyclic junction requires single-crystal X-ray diffraction study to determine the stereochemistry of the product (Shanmugasundaram et al., 2002)

In the title compound (Fig. 1) the O--benzyl groups are all in equatorial positions. The pyran ring adopts a twist-boat conformation with ring puckering parameters of q₂ = 0.6935 (15) Å, q₃ = -0.1106 (16) Å, Q = 0.7023 (16) Å and ϕ₂ = 342.07 (14)° (Cremer & Pople, 1975). Strong O—H···O hydrogen bonding create infinite one-dimensional chains along the [100] direction. Several weak C—H···O/Cl/Cg interactions are also noted and listed in Table 1.

Related literature top

For O-benzyl deprotection methodologies, see: Akiyama et al. (1991). For a related structure, see: Shanmugasundaram et al. (2002). For ring puckering analysis, see: Cremer & Pople (1975).

Experimental top

AlCl₃ (37 mg, 0.28 mmol) was added to a solution of dichlorocyclopropyl sugar derivative (see A in scheme 2)(100 mg, 0.20 mmol) in toluene (1 ml) and the resulting mixture was stirred for 2 h at room temperature. The reaction mixture was then diluted with water and the aqueous phase was extracted with toluene. 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 dichlorocyclopropyl sugar derivative I in 73% yield as a white solid.

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); 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. A view of the title compound; displacement ellipsoids are drawn at 50% probability level.
	Fig. 2. Reaction scheme for the dihalocarbene cyclopropanation of the protected glucal.

1,5-Anhydro-3,6-di-O-benzyl-2-deoxy-1,2-C-dichloromethylene- D-glycero-D-gulo-hexitol top

Crystal data top

C₂₁H₂₂Cl₂O₄	F(000) = 856
M_r = 409.29	D_x = 1.389 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 8719 reflections
a = 5.2985 (1) Å	θ = 4.5–64.5°
b = 18.8511 (3) Å	µ = 3.19 mm⁻¹
c = 19.5973 (4) Å	T = 100 K
V = 1957.43 (6) Å³	Needle, colorless
Z = 4	0.16 × 0.06 × 0.05 mm

Data collection top

Bruker APEX DUO 4K CCD diffractometer	3241 independent reflections
Incoatec Quazar Multilayer Mirror monochromator	3108 reflections with I > 2σ(I)
Detector resolution: 8.4 pixels mm^-1	R_int = 0.038
ϕ and ω scans	θ_max = 64.9°, θ_min = 4.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −3→6
T_min = 0.630, T_max = 0.857	k = −21→22
14434 measured reflections	l = −22→22

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) = 0.055	w = 1/[σ²(F_o²) + (0.0249P)² + 0.1406P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3241 reflections	Δρ_max = 0.14 e Å⁻³
245 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1327 Friedel Pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.009 (9)

Crystal data top

C₂₁H₂₂Cl₂O₄	V = 1957.43 (6) Å³
M_r = 409.29	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 5.2985 (1) Å	µ = 3.19 mm⁻¹
b = 18.8511 (3) Å	T = 100 K
c = 19.5973 (4) Å	0.16 × 0.06 × 0.05 mm

Data collection top

Bruker APEX DUO 4K CCD diffractometer	3241 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	3108 reflections with I > 2σ(I)
T_min = 0.630, T_max = 0.857	R_int = 0.038
14434 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	H-atom parameters constrained
wR(F²) = 0.055	Δρ_max = 0.14 e Å⁻³
S = 1.05	Δρ_min = −0.19 e Å⁻³
3241 reflections	Absolute structure: Flack (1983), 1327 Friedel Pairs
245 parameters	Absolute structure parameter: 0.009 (9)
0 restraints

Special details top

Experimental. The intensity data was collected on a Bruker Apex DUO 4 K CCD diffractometer using an exposure time of 10 s/frame. A total of 1989 frames were collected with a frame width of 1° covering up to θ = 64.94° with 97.8% completeness accomplished.

Analytical data: mp 91–93 °C; ¹H NMR (CDCl₃, 400 MHz) δ 7.50–7.20 (m, 10H), 4.77 (d, J = 11.7 Hz, 1H), 4.61–4.50 (m, 3H), 3.90–3.80 (m, 4H), 3.65 (dd, J = 1.5 and 3.3 Hz, 1H), 3.56 (dd, J = 4.4 and 9.2 Hz, 1H), 2.59 (bs, 1H), 1.73 (dd, J = 4.6 and 8.2 Hz, 1H); ¹³C NMR (CDCl₃, 75 MHz) δ 137.9, 137.1, 128.6, 128.4, 128.2, 127.7, 127.6, 79.2, 76.4, 73.5, 71.9, 70.5, 68.3, 58.9, 33.2.

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	0.5355 (4)	1.08839 (10)	0.90087 (9)	0.0335 (4)
H1	0.4672	1.0591	0.866	0.04*
C2	0.7181 (4)	1.13816 (11)	0.88478 (10)	0.0425 (5)
H2	0.7732	1.143	0.8389	0.051*
C3	0.8206 (4)	1.18073 (11)	0.93482 (10)	0.0354 (5)
H3	0.9442	1.2153	0.9234	0.042*
C4	0.7428 (3)	1.17297 (9)	1.00165 (9)	0.0292 (4)
H4	0.8145	1.2017	1.0365	0.035*
C6	0.5596 (3)	1.12310 (9)	1.01784 (9)	0.0287 (4)
H6	0.5073	1.1177	1.0639	0.034*
C7	0.4516 (3)	1.08095 (9)	0.96753 (9)	0.0242 (4)
C8	0.2384 (4)	1.03164 (9)	0.98508 (9)	0.0277 (4)
H8A	0.2523	1.017	1.0335	0.033*
H8B	0.0754	1.0565	0.979	0.033*
C9	0.0295 (3)	0.92729 (9)	0.95300 (8)	0.0228 (4)
H9A	−0.1252	0.9554	0.9444	0.027*
H9B	0.0258	0.9108	1.0009	0.027*
C10	0.0368 (3)	0.86420 (8)	0.90551 (8)	0.0190 (3)
H10	−0.1134	0.8344	0.917	0.023*
C11	0.2697 (3)	0.81673 (8)	0.91569 (8)	0.0169 (3)
H11	0.417	0.8468	0.9292	0.02*
C12	0.3303 (3)	0.77835 (8)	0.84966 (8)	0.0165 (3)
H12	0.1789	0.7518	0.8331	0.02*
C13	0.4032 (3)	0.83516 (8)	0.79898 (8)	0.0175 (3)
H13	0.5868	0.8472	0.7966	0.021*
C14	0.2225 (3)	0.89727 (8)	0.79761 (8)	0.0193 (3)
H14	0.2957	0.9461	0.7955	0.023*
C15	0.2516 (3)	0.85065 (9)	0.73630 (8)	0.0198 (3)
C16	0.5667 (3)	0.68293 (8)	0.80641 (8)	0.0190 (3)
H16A	0.6067	0.7097	0.7643	0.023*
H16B	0.4088	0.6561	0.7985	0.023*
C17	0.7775 (3)	0.63247 (8)	0.82228 (8)	0.0192 (3)
C18	0.8761 (3)	0.62666 (9)	0.88720 (9)	0.0258 (4)
H18	0.8135	0.6562	0.9227	0.031*
C19	1.0653 (4)	0.57824 (11)	0.90107 (11)	0.0381 (5)
H19	1.1307	0.5746	0.9461	0.046*
C20	1.1593 (3)	0.53552 (10)	0.85055 (12)	0.0404 (5)
H20	1.2892	0.5024	0.8605	0.048*
C21	1.0652 (3)	0.54082 (10)	0.78545 (12)	0.0401 (5)
H21	1.1301	0.5113	0.7503	0.048*
C22	0.8757 (3)	0.58918 (10)	0.77109 (10)	0.0319 (4)
H22	0.812	0.5929	0.7259	0.038*
O1	0.2452 (2)	0.97025 (6)	0.94223 (6)	0.0233 (3)
O2	0.00229 (19)	0.88752 (6)	0.83550 (5)	0.0204 (2)
O3	0.2084 (2)	0.76993 (6)	0.97025 (5)	0.0212 (3)
H3A	0.3402	0.7498	0.9841	0.032*
O4	0.5327 (2)	0.73099 (5)	0.86182 (5)	0.0177 (2)
Cl1	0.41378 (7)	0.88614 (2)	0.66614 (2)	0.02898 (11)
Cl2	0.00637 (7)	0.79466 (2)	0.711124 (19)	0.02339 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0449 (12)	0.0313 (10)	0.0242 (9)	−0.0091 (9)	−0.0094 (8)	−0.0001 (8)
C2	0.0609 (14)	0.0429 (12)	0.0238 (10)	−0.0156 (11)	−0.0032 (10)	0.0071 (9)
C3	0.0414 (11)	0.0277 (10)	0.0370 (11)	−0.0071 (9)	−0.0040 (8)	0.0040 (9)
C4	0.0328 (11)	0.0236 (9)	0.0312 (10)	0.0032 (8)	−0.0041 (8)	−0.0067 (8)
C6	0.0321 (10)	0.0271 (10)	0.0270 (9)	0.0047 (8)	0.0042 (7)	−0.0073 (8)
C7	0.0249 (10)	0.0191 (9)	0.0286 (9)	0.0066 (7)	−0.0018 (7)	−0.0017 (7)
C8	0.0302 (10)	0.0220 (9)	0.0309 (10)	0.0035 (8)	0.0049 (8)	−0.0091 (8)
C9	0.0180 (9)	0.0255 (9)	0.0248 (9)	0.0044 (7)	0.0039 (7)	0.0002 (7)
C10	0.0153 (8)	0.0219 (8)	0.0197 (8)	0.0009 (7)	0.0019 (6)	0.0030 (6)
C11	0.0134 (8)	0.0182 (8)	0.0192 (8)	−0.0015 (7)	−0.0013 (6)	0.0021 (6)
C12	0.0118 (8)	0.0184 (8)	0.0193 (8)	0.0006 (6)	−0.0017 (6)	0.0011 (7)
C13	0.0126 (7)	0.0194 (8)	0.0206 (8)	−0.0007 (6)	0.0001 (6)	0.0026 (7)
C14	0.0159 (8)	0.0188 (8)	0.0231 (8)	−0.0007 (6)	−0.0010 (6)	0.0025 (7)
C15	0.0165 (8)	0.0216 (9)	0.0212 (8)	−0.0017 (7)	−0.0001 (6)	0.0047 (7)
C16	0.0207 (8)	0.0171 (8)	0.0192 (8)	−0.0007 (6)	−0.0016 (6)	−0.0012 (6)
C17	0.0155 (8)	0.0145 (8)	0.0277 (9)	−0.0041 (6)	0.0024 (7)	−0.0010 (7)
C18	0.0231 (9)	0.0281 (10)	0.0261 (9)	0.0049 (8)	0.0015 (7)	0.0037 (8)
C19	0.0298 (11)	0.0417 (12)	0.0429 (12)	0.0095 (9)	−0.0045 (8)	0.0103 (10)
C20	0.0234 (10)	0.0260 (10)	0.0717 (16)	0.0089 (8)	−0.0016 (9)	0.0021 (11)
C21	0.0231 (10)	0.0260 (10)	0.0712 (15)	0.0002 (8)	0.0070 (10)	−0.0215 (10)
C22	0.0234 (9)	0.0328 (10)	0.0395 (11)	−0.0008 (8)	−0.0024 (8)	−0.0179 (8)
O1	0.0220 (6)	0.0199 (6)	0.0280 (6)	0.0017 (5)	0.0058 (5)	−0.0077 (5)
O2	0.0156 (5)	0.0245 (6)	0.0210 (5)	0.0039 (5)	−0.0006 (4)	0.0016 (5)
O3	0.0197 (6)	0.0251 (6)	0.0188 (6)	0.0016 (5)	0.0013 (5)	0.0058 (5)
O4	0.0183 (6)	0.0179 (5)	0.0170 (5)	0.0036 (5)	−0.0025 (4)	−0.0011 (4)
Cl1	0.0229 (2)	0.0396 (3)	0.0245 (2)	−0.00114 (19)	0.00327 (16)	0.0137 (2)
Cl2	0.01837 (19)	0.0297 (2)	0.02214 (19)	−0.00268 (17)	−0.00245 (15)	−0.00181 (16)

Geometric parameters (Å, º) top

C1—C2	1.384 (3)	C12—C13	1.511 (2)
C1—C7	1.387 (3)	C12—H12	1
C1—H1	0.95	C13—C15	1.496 (2)
C2—C3	1.379 (3)	C13—C14	1.513 (2)
C2—H2	0.95	C13—H13	1
C3—C4	1.381 (3)	C14—O2	1.3950 (19)
C3—H3	0.95	C14—C15	1.497 (2)
C4—C6	1.388 (3)	C14—H14	1
C4—H4	0.95	C15—Cl2	1.7452 (16)
C6—C7	1.389 (2)	C15—Cl1	1.7541 (16)
C6—H6	0.95	C16—O4	1.4254 (18)
C7—C8	1.503 (3)	C16—C17	1.500 (2)
C8—O1	1.4303 (19)	C16—H16A	0.99
C8—H8A	0.99	C16—H16B	0.99
C8—H8B	0.99	C17—C18	1.380 (2)
C9—O1	1.416 (2)	C17—C22	1.394 (2)
C9—C10	1.511 (2)	C18—C19	1.383 (2)
C9—H9A	0.99	C18—H18	0.95
C9—H9B	0.99	C19—C20	1.370 (3)
C10—O2	1.4523 (18)	C19—H19	0.95
C10—C11	1.538 (2)	C20—C21	1.373 (3)
C10—H10	1	C20—H20	0.95
C11—O3	1.4239 (18)	C21—C22	1.385 (3)
C11—C12	1.517 (2)	C21—H21	0.95
C11—H11	1	C22—H22	0.95
C12—O4	1.4157 (18)	O3—H3A	0.84

C2—C1—C7	120.47 (17)	C11—C12—H12	110.3
C2—C1—H1	119.8	C15—C13—C12	122.73 (13)
C7—C1—H1	119.8	C15—C13—C14	59.65 (10)
C3—C2—C1	120.52 (19)	C12—C13—C14	113.49 (13)
C3—C2—H2	119.7	C15—C13—H13	116.1
C1—C2—H2	119.7	C12—C13—H13	116.1
C2—C3—C4	119.70 (19)	C14—C13—H13	116.1
C2—C3—H3	120.2	O2—C14—C15	115.86 (13)
C4—C3—H3	120.2	O2—C14—C13	114.71 (13)
C3—C4—C6	119.82 (17)	C15—C14—C13	59.64 (10)
C3—C4—H4	120.1	O2—C14—H14	117.9
C6—C4—H4	120.1	C15—C14—H14	117.9
C4—C6—C7	120.86 (16)	C13—C14—H14	117.9
C4—C6—H6	119.6	C13—C15—C14	60.72 (10)
C7—C6—H6	119.6	C13—C15—Cl2	120.91 (11)
C1—C7—C6	118.60 (17)	C14—C15—Cl2	120.36 (11)
C1—C7—C8	121.26 (16)	C13—C15—Cl1	117.06 (11)
C6—C7—C8	120.05 (16)	C14—C15—Cl1	117.12 (11)
O1—C8—C7	110.31 (13)	Cl2—C15—Cl1	111.95 (9)
O1—C8—H8A	109.6	O4—C16—C17	109.83 (12)
C7—C8—H8A	109.6	O4—C16—H16A	109.7
O1—C8—H8B	109.6	C17—C16—H16A	109.7
C7—C8—H8B	109.6	O4—C16—H16B	109.7
H8A—C8—H8B	108.1	C17—C16—H16B	109.7
O1—C9—C10	109.73 (12)	H16A—C16—H16B	108.2
O1—C9—H9A	109.7	C18—C17—C22	118.41 (16)
C10—C9—H9A	109.7	C18—C17—C16	121.58 (14)
O1—C9—H9B	109.7	C22—C17—C16	120.01 (15)
C10—C9—H9B	109.7	C17—C18—C19	120.55 (17)
H9A—C9—H9B	108.2	C17—C18—H18	119.7
O2—C10—C9	109.91 (12)	C19—C18—H18	119.7
O2—C10—C11	113.57 (12)	C20—C19—C18	120.64 (19)
C9—C10—C11	113.50 (13)	C20—C19—H19	119.7
O2—C10—H10	106.4	C18—C19—H19	119.7
C9—C10—H10	106.4	C19—C20—C21	119.78 (18)
C11—C10—H10	106.4	C19—C20—H20	120.1
O3—C11—C12	113.16 (12)	C21—C20—H20	120.1
O3—C11—C10	105.95 (12)	C20—C21—C22	119.98 (18)
C12—C11—C10	109.68 (12)	C20—C21—H21	120
O3—C11—H11	109.3	C22—C21—H21	120
C12—C11—H11	109.3	C21—C22—C17	120.65 (18)
C10—C11—H11	109.3	C21—C22—H22	119.7
O4—C12—C13	111.35 (12)	C17—C22—H22	119.7
O4—C12—C11	108.51 (12)	C9—O1—C8	110.77 (12)
C13—C12—C11	106.06 (12)	C14—O2—C10	115.94 (11)
O4—C12—H12	110.3	C11—O3—H3A	109.5
C13—C12—H12	110.3	C12—O4—C16	111.61 (11)

C7—C1—C2—C3	0.5 (3)	C12—C13—C15—Cl2	−9.9 (2)
C1—C2—C3—C4	0.9 (3)	C14—C13—C15—Cl2	−109.85 (14)
C2—C3—C4—C6	−0.9 (3)	C12—C13—C15—Cl1	−152.58 (12)
C3—C4—C6—C7	−0.4 (3)	C14—C13—C15—Cl1	107.49 (13)
C2—C1—C7—C6	−1.7 (3)	O2—C14—C15—C13	−104.74 (15)
C2—C1—C7—C8	174.77 (17)	O2—C14—C15—Cl2	6.00 (19)
C4—C6—C7—C1	1.7 (3)	C13—C14—C15—Cl2	110.74 (14)
C4—C6—C7—C8	−174.85 (16)	O2—C14—C15—Cl1	147.88 (11)
C1—C7—C8—O1	34.7 (2)	C13—C14—C15—Cl1	−107.39 (13)
C6—C7—C8—O1	−148.89 (15)	O4—C16—C17—C18	12.7 (2)
O1—C9—C10—O2	−68.30 (16)	O4—C16—C17—C22	−168.31 (14)
O1—C9—C10—C11	60.10 (17)	C22—C17—C18—C19	−0.9 (2)
O2—C10—C11—O3	−149.38 (12)	C16—C17—C18—C19	178.06 (16)
C9—C10—C11—O3	84.13 (15)	C17—C18—C19—C20	0.4 (3)
O2—C10—C11—C12	−26.92 (18)	C18—C19—C20—C21	0.1 (3)
C9—C10—C11—C12	−153.42 (13)	C19—C20—C21—C22	−0.1 (3)
O3—C11—C12—O4	−57.46 (16)	C20—C21—C22—C17	−0.4 (3)
C10—C11—C12—O4	−175.51 (12)	C18—C17—C22—C21	0.9 (3)
O3—C11—C12—C13	−177.19 (12)	C16—C17—C22—C21	−178.06 (16)
C10—C11—C12—C13	64.76 (16)	C10—C9—O1—C8	178.08 (13)
O4—C12—C13—C15	126.95 (15)	C7—C8—O1—C9	−173.42 (14)
C11—C12—C13—C15	−115.19 (16)	C15—C14—O2—C10	117.76 (14)
O4—C12—C13—C14	−165.12 (12)	C13—C14—O2—C10	51.05 (17)
C11—C12—C13—C14	−47.26 (17)	C9—C10—O2—C14	96.56 (15)
C15—C13—C14—O2	106.67 (15)	C11—C10—O2—C14	−31.80 (18)
C12—C13—C14—O2	−8.71 (19)	C13—C12—O4—C16	−75.51 (15)
C12—C13—C14—C15	−115.39 (15)	C11—C12—O4—C16	168.12 (12)
C12—C13—C15—C14	99.94 (16)	C17—C16—O4—C12	−178.33 (12)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C1–C7 and C17–C22 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O3ⁱ	0.84	2.18	2.9905 (10)	163
C11—H11···O1	1.00	2.51	2.9433 (19)	106
C12—H12···Cl2	1.00	2.68	3.2266 (15)	114
C13—H13···O2ⁱⁱ	1.00	2.45	3.4005 (19)	158
C18—H18···O4	0.95	2.37	2.725 (2)	102
C18—H18···O3ⁱ	0.95	2.58	3.521 (2)	171
C20—H20···Cl1ⁱⁱⁱ	0.95	2.75	3.6268 (19)	154
C8—H8B···Cg1^iv	0.99	2.76	3.7480 (18)	175
C16—H16B···Cg2^iv	0.99	2.79	3.7195 (17)	156

Symmetry codes: (i) x+1/2, −y+3/2, −z+2; (ii) x+1, y, z; (iii) −x+2, y−1/2, −z+3/2; (iv) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₂₁H₂₂Cl₂O₄
M_r	409.29
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	5.2985 (1), 18.8511 (3), 19.5973 (4)
V (Å³)	1957.43 (6)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	3.19
Crystal size (mm)	0.16 × 0.06 × 0.05

Data collection
Diffractometer	Bruker APEX DUO 4K CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.630, 0.857
No. of measured, independent and observed [I > 2σ(I)] reflections	14434, 3241, 3108
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.588

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.055, 1.05
No. of reflections	3241
No. of parameters	245
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.19
Absolute structure	Flack (1983), 1327 Friedel Pairs
Absolute structure parameter	0.009 (9)

Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2008), SAINT and XPREP (Bruker, 2008), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C1–C7 and C17–C22 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O3ⁱ	0.84	2.18	2.9905 (10)	162.7
C13—H13···O2ⁱⁱ	1.00	2.45	3.4005 (19)	158.4
C18—H18···O3ⁱ	0.95	2.58	3.521 (2)	170.7
C20—H20···Cl1ⁱⁱⁱ	0.95	2.75	3.6268 (19)	154.2
C8—H8B···Cg1^iv	0.99	2.76	3.7480 (18)	175
C16—H16B···Cg2^iv	0.99	2.79	3.7195 (17)	156

Symmetry codes: (i) x+1/2, −y+3/2, −z+2; (ii) x+1, y, z; (iii) −x+2, y−1/2, −z+3/2; (iv) x−1, y, z.

Acknowledgements

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

References

Akiyama, T., Hirofuji, H. & Ozaki, S. (1991). Tetrahedron Lett. 32, 1321–1324. CrossRef CAS Web of Science Google Scholar
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2008). SADABS, SAINT and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2011). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Shanmugasundaram, B., Varghese, B. & Balasubramanian, K. K. (2002). Carbohydr. Res. 337, 1523–1527. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2888

doi:10.1107/S1600536811040815

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

1,5-Anhydro-3,6-di-O-benzyl-2-de­­oxy-1,2-C-di­chloro­methyl­ene-D-glycero-D-gulo-hexitol

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

1,5-Anhydro-3,6-di-O-benzyl-2-deoxy-1,2-C-dichloromethylene-D-glycero-D-gulo-hexitol