Methyl 2,3-di-O-acetyl-4-O-levulinoyl-1-O-(2,2,2-trichloro-2-imino-ethyl)-l-ido-pyran-osiduronate.

In the title compound, C(18)H(22)Cl(3)NO(11), a novel derivative of l-idopyran-osiduronic acid, the six-membered ring adopts a chair conformation.

Related literature

For background to l-iduronic acids, see: Capila & Linhardt (2002 ▶); Jobron & Jacquinet (1998 ▶); Lee et al. (2004 ▶). For the synthesis of iduronic acid derivatives, see: Yu et al. (2004 ▶); Sanjoy et al. (2001 ▶); Lubineau et al. (2000 ▶); Lohman et al. (2003 ▶).

Experimental

Crystal data

C18H22Cl3NO11

M = 534.72

Orthorhombic,

a = 9.0498 (10) Å

b = 9.7560 (11) Å

c = 26.570 (3) Å

V = 2345.8 (4) Å3

Z = 4

Cu Kα radiation

μ = 4.07 mm−1

T = 173 K

0.41 × 0.30 × 0.28 mm

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer

Absorption correction: numerical (ABSCOR; Higashi, 1995 ▶) T min = 0.286, T max = 0.395

16340 measured reflections

4259 independent reflections

3893 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.100

S = 1.09

4259 reflections

302 parameters

H-atom parameters constrained

Δρmax = 0.45 e Å−3

Δρmin = −0.48 e Å−3

Absolute structure: Flack (1983 ▶), 1804 Friedel pairs

Flack parameter: 0.023 (18)

Data collection: RAPID-AUTO (Rigaku, 2001 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810010895/bt5207sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810010895/bt5207Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C18H22Cl3NO11	Dx = 1.514 Mg m−3
Mr = 534.72	Cu Kα radiation, λ = 1.54186 Å
Orthorhombic, P212121	Cell parameters from 1098 reflections
a = 9.0498 (10) Å	θ = 2.2–27.5°
b = 9.7560 (11) Å	µ = 4.07 mm−1
c = 26.570 (3) Å	T = 173 K
V = 2345.8 (4) Å3	Block, colorless
Z = 4	0.41 × 0.30 × 0.28 mm
F(000) = 1104

Rigaku R-AXIS RAPID IP area-detector diffractometer	4259 independent reflections
Radiation source: rotating anode	3893 reflections with I > 2σ(I)
graphite	Rint = 0.047
ω scans at fixed χ = 45°	θmax = 68.2°, θmin = 3.3°
Absorption correction: numerical (ABSCOR; Higashi, 1995)	h = −10→10
Tmin = 0.286, Tmax = 0.395	k = −11→11
16340 measured reflections	l = −32→31

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)] = 0.046	H-atom parameters constrained
wR(F2) = 0.100	w = 1/[σ2(Fo2) + (0.0268P)2 + 1.8534P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
4259 reflections	Δρmax = 0.45 e Å−3
302 parameters	Δρmin = −0.48 e Å−3
0 restraints	Absolute structure: Flack (1983), 1804 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.023 (18)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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.

	x	y	z	Uiso*/Ueq
Cl1	0.43622 (11)	0.42769 (10)	−0.00915 (3)	0.0470 (2)
Cl2	0.44529 (14)	0.72085 (10)	−0.00601 (4)	0.0578 (3)
Cl3	0.62102 (10)	0.56765 (16)	0.06361 (4)	0.0664 (3)
O1	0.2587 (2)	0.4459 (2)	0.17647 (7)	0.0275 (5)
O2	0.3250 (2)	0.4443 (2)	0.09152 (8)	0.0329 (5)
O3	0.0181 (2)	0.2548 (2)	0.14357 (8)	0.0332 (5)
O4	−0.0977 (3)	0.3313 (3)	0.07477 (9)	0.0527 (7)
O5	0.3933 (2)	0.1578 (2)	0.10987 (8)	0.0320 (5)
O6	0.2917 (3)	−0.0176 (3)	0.06774 (10)	0.0488 (7)
O7	0.1922 (2)	0.1967 (2)	0.22751 (8)	0.0285 (5)
O8	0.2316 (3)	−0.0295 (2)	0.23558 (11)	0.0493 (7)
O9	0.1750 (4)	0.1508 (4)	0.35252 (12)	0.0780 (11)
O10	0.3492 (3)	0.4899 (3)	0.27135 (9)	0.0462 (7)
O11	0.4850 (3)	0.2966 (3)	0.26989 (8)	0.0402 (6)
N1	0.2424 (3)	0.6658 (3)	0.08223 (11)	0.0411 (7)
H1A	0.2761	0.7351	0.0630	0.049*
C1	0.2099 (3)	0.4196 (4)	0.12743 (10)	0.0284 (7)
H1C	0.1257	0.4827	0.1198	0.034*
C2	0.1588 (3)	0.2725 (3)	0.11851 (12)	0.0280 (7)
H2A	0.1470	0.2558	0.0816	0.034*
C3	0.2619 (3)	0.1663 (3)	0.14075 (11)	0.0269 (7)
H3A	0.2117	0.0751	0.1419	0.032*
C4	0.3162 (4)	0.2048 (3)	0.19295 (11)	0.0260 (7)
H4A	0.3971	0.1416	0.2038	0.031*
C5	0.3679 (4)	0.3526 (3)	0.19531 (11)	0.0271 (7)
H5A	0.4609	0.3628	0.1754	0.033*
C6	0.3286 (4)	0.5705 (4)	0.06991 (11)	0.0315 (7)
C7	0.4526 (4)	0.5722 (4)	0.03110 (11)	0.0352 (7)
C8	−0.1037 (4)	0.2905 (4)	0.11727 (13)	0.0366 (8)
C9	−0.2403 (4)	0.2721 (4)	0.14798 (15)	0.0458 (10)
H9A	−0.3271	0.2931	0.1273	0.069*
H9B	−0.2373	0.3341	0.1770	0.069*
H9C	−0.2461	0.1771	0.1598	0.069*
C10	0.3914 (4)	0.0610 (4)	0.07321 (11)	0.0343 (7)
C11	0.5308 (4)	0.0652 (4)	0.04323 (13)	0.0471 (9)
H11A	0.5075	0.0543	0.0074	0.071*
H11B	0.5962	−0.0092	0.0540	0.071*
H11C	0.5802	0.1535	0.0485	0.071*
C12	0.1578 (4)	0.0694 (4)	0.24437 (11)	0.0323 (7)
C13	0.0114 (4)	0.0687 (4)	0.27120 (12)	0.0350 (7)
H13A	0.0108	−0.0084	0.2954	0.042*
H13B	−0.0674	0.0511	0.2462	0.042*
C14	−0.0258 (4)	0.1992 (4)	0.29934 (12)	0.0349 (8)
H14A	−0.0291	0.2762	0.2751	0.042*
H14B	−0.1254	0.1898	0.3143	0.042*
C15	0.0820 (4)	0.2329 (4)	0.34006 (13)	0.0434 (9)
C16	0.0726 (6)	0.3724 (4)	0.36322 (14)	0.0572 (12)
H16A	0.1519	0.3832	0.3881	0.086*
H16B	−0.0233	0.3832	0.3799	0.086*
H16C	0.0832	0.4422	0.3369	0.086*
C17	0.3974 (4)	0.3918 (3)	0.24983 (12)	0.0308 (7)
C18	0.5206 (4)	0.3098 (4)	0.32281 (13)	0.0481 (10)
H18A	0.5860	0.2346	0.3329	0.072*
H18B	0.4295	0.3062	0.3427	0.072*
H18C	0.5705	0.3975	0.3286	0.072*

	U11	U22	U33	U12	U13	U23
Cl1	0.0627 (6)	0.0425 (5)	0.0358 (4)	−0.0035 (5)	0.0135 (4)	−0.0068 (4)
Cl2	0.0917 (8)	0.0412 (5)	0.0405 (5)	−0.0004 (5)	0.0219 (5)	0.0099 (4)
Cl3	0.0339 (5)	0.1146 (10)	0.0507 (5)	−0.0158 (6)	−0.0041 (4)	0.0145 (7)
O1	0.0301 (11)	0.0272 (12)	0.0252 (10)	0.0002 (10)	0.0028 (9)	−0.0002 (9)
O2	0.0336 (12)	0.0322 (13)	0.0330 (11)	0.0029 (11)	0.0122 (10)	0.0045 (10)
O3	0.0228 (12)	0.0440 (14)	0.0328 (11)	−0.0007 (11)	0.0049 (10)	−0.0025 (10)
O4	0.0407 (15)	0.079 (2)	0.0381 (15)	0.0149 (15)	−0.0022 (12)	−0.0001 (14)
O5	0.0287 (12)	0.0353 (13)	0.0321 (11)	−0.0007 (10)	0.0113 (10)	−0.0070 (10)
O6	0.0489 (16)	0.0484 (16)	0.0492 (15)	−0.0084 (14)	0.0079 (13)	−0.0188 (13)
O7	0.0303 (12)	0.0276 (12)	0.0276 (11)	−0.0022 (10)	0.0105 (10)	0.0035 (9)
O8	0.0546 (17)	0.0269 (14)	0.0664 (18)	0.0040 (13)	0.0261 (15)	0.0048 (12)
O9	0.079 (2)	0.089 (3)	0.067 (2)	0.029 (2)	−0.0329 (19)	−0.0091 (19)
O10	0.0583 (17)	0.0445 (16)	0.0359 (13)	0.0033 (14)	−0.0002 (13)	−0.0117 (12)
O11	0.0410 (14)	0.0437 (14)	0.0358 (12)	0.0008 (12)	−0.0087 (11)	0.0005 (11)
N1	0.052 (2)	0.0306 (16)	0.0402 (16)	0.0008 (16)	0.0072 (15)	0.0049 (13)
C1	0.0252 (15)	0.0342 (17)	0.0259 (14)	−0.0011 (15)	0.0053 (12)	0.0028 (15)
C2	0.0214 (15)	0.0346 (18)	0.0281 (16)	−0.0045 (15)	0.0052 (13)	−0.0032 (14)
C3	0.0249 (16)	0.0300 (17)	0.0258 (15)	−0.0021 (14)	0.0094 (13)	−0.0001 (13)
C4	0.0266 (16)	0.0278 (17)	0.0236 (15)	−0.0022 (14)	0.0063 (13)	−0.0010 (13)
C5	0.0237 (16)	0.0273 (16)	0.0304 (16)	−0.0014 (14)	0.0025 (14)	0.0014 (13)
C6	0.0374 (17)	0.0334 (18)	0.0237 (15)	0.0014 (17)	−0.0004 (13)	0.0029 (15)
C7	0.0366 (18)	0.0417 (19)	0.0273 (15)	−0.0030 (18)	−0.0002 (14)	0.0004 (15)
C8	0.0291 (18)	0.043 (2)	0.0373 (19)	−0.0020 (17)	0.0018 (15)	−0.0103 (16)
C9	0.0248 (19)	0.055 (2)	0.058 (2)	−0.0024 (18)	0.0058 (17)	−0.006 (2)
C10	0.0381 (18)	0.0355 (18)	0.0295 (16)	0.0043 (18)	0.0005 (14)	−0.0050 (15)
C11	0.050 (2)	0.050 (2)	0.0415 (19)	0.002 (2)	0.0182 (17)	−0.0085 (19)
C12	0.0360 (18)	0.0289 (17)	0.0319 (16)	−0.0055 (17)	0.0062 (14)	0.0035 (15)
C13	0.0318 (17)	0.0350 (18)	0.0383 (17)	−0.0042 (17)	0.0068 (14)	0.0049 (16)
C14	0.0305 (18)	0.0380 (19)	0.0363 (17)	0.0014 (16)	0.0072 (15)	0.0054 (15)
C15	0.048 (2)	0.055 (2)	0.0276 (17)	0.002 (2)	0.0040 (17)	0.0029 (17)
C16	0.075 (3)	0.058 (3)	0.039 (2)	−0.008 (2)	0.007 (2)	−0.0088 (18)
C17	0.0275 (16)	0.0347 (19)	0.0301 (16)	−0.0089 (15)	0.0022 (14)	−0.0008 (14)
C18	0.047 (2)	0.065 (3)	0.0320 (18)	−0.011 (2)	−0.0091 (17)	0.0113 (18)

Cl1—C7	1.776 (4)	C4—C5	1.517 (4)
Cl2—C7	1.754 (4)	C4—H4A	1.0000
Cl3—C7	1.753 (3)	C5—C17	1.522 (4)
O1—C1	1.399 (3)	C5—H5A	1.0000
O1—C5	1.433 (4)	C6—C7	1.524 (4)
O2—C6	1.359 (4)	C8—C9	1.492 (5)
O2—C1	1.433 (3)	C9—H9A	0.9800
O3—C8	1.351 (4)	C9—H9B	0.9800
O3—C2	1.447 (3)	C9—H9C	0.9800
O4—C8	1.199 (4)	C10—C11	1.492 (4)
O5—C10	1.357 (4)	C11—H11A	0.9800
O5—C3	1.447 (3)	C11—H11B	0.9800
O6—C10	1.194 (4)	C11—H11C	0.9800
O7—C12	1.356 (4)	C12—C13	1.504 (4)
O7—C4	1.452 (3)	C13—C14	1.515 (5)
O8—C12	1.197 (4)	C13—H13A	0.9900
O9—C15	1.208 (5)	C13—H13B	0.9900
O10—C17	1.197 (4)	C14—C15	1.493 (5)
O11—C17	1.333 (4)	C14—H14A	0.9900
O11—C18	1.448 (4)	C14—H14B	0.9900
N1—C6	1.256 (4)	C15—C16	1.496 (5)
N1—H1A	0.9001	C16—H16A	0.9800
C1—C2	1.527 (4)	C16—H16B	0.9800
C1—H1C	1.0000	C16—H16C	0.9800
C2—C3	1.514 (4)	C18—H18A	0.9800
C2—H2A	1.0000	C18—H18B	0.9800
C3—C4	1.518 (4)	C18—H18C	0.9800
C3—H3A	1.0000
C1—O1—C5	115.3 (2)	C8—C9—H9A	109.5
C6—O2—C1	116.8 (2)	C8—C9—H9B	109.5
C8—O3—C2	116.7 (2)	H9A—C9—H9B	109.5
C10—O5—C3	115.9 (2)	C8—C9—H9C	109.5
C12—O7—C4	115.9 (2)	H9A—C9—H9C	109.5
C17—O11—C18	117.3 (3)	H9B—C9—H9C	109.5
C6—N1—H1A	101.4	O6—C10—O5	123.0 (3)
O1—C1—O2	111.1 (2)	O6—C10—C11	126.3 (3)
O1—C1—C2	114.3 (3)	O5—C10—C11	110.7 (3)
O2—C1—C2	105.9 (2)	C10—C11—H11A	109.5
O1—C1—H1C	108.4	C10—C11—H11B	109.5
O2—C1—H1C	108.4	H11A—C11—H11B	109.5
C2—C1—H1C	108.4	C10—C11—H11C	109.5
O3—C2—C3	106.3 (2)	H11A—C11—H11C	109.5
O3—C2—C1	107.9 (2)	H11B—C11—H11C	109.5
C3—C2—C1	113.3 (3)	O8—C12—O7	123.1 (3)
O3—C2—H2A	109.7	O8—C12—C13	125.5 (3)
C3—C2—H2A	109.7	O7—C12—C13	111.3 (3)
C1—C2—H2A	109.7	C12—C13—C14	115.2 (3)
O5—C3—C2	108.9 (2)	C12—C13—H13A	108.5
O5—C3—C4	105.4 (2)	C14—C13—H13A	108.5
C2—C3—C4	112.8 (3)	C12—C13—H13B	108.5
O5—C3—H3A	109.9	C14—C13—H13B	108.5
C2—C3—H3A	109.9	H13A—C13—H13B	107.5
C4—C3—H3A	109.9	C15—C14—C13	113.4 (3)
O7—C4—C5	105.3 (2)	C15—C14—H14A	108.9
O7—C4—C3	108.3 (2)	C13—C14—H14A	108.9
C5—C4—C3	111.9 (3)	C15—C14—H14B	108.9
O7—C4—H4A	110.4	C13—C14—H14B	108.9
C5—C4—H4A	110.4	H14A—C14—H14B	107.7
C3—C4—H4A	110.4	O9—C15—C14	120.5 (4)
O1—C5—C4	112.1 (3)	O9—C15—C16	122.0 (4)
O1—C5—C17	107.1 (3)	C14—C15—C16	117.5 (4)
C4—C5—C17	109.4 (3)	C15—C16—H16A	109.5
O1—C5—H5A	109.4	C15—C16—H16B	109.5
C4—C5—H5A	109.4	H16A—C16—H16B	109.5
C17—C5—H5A	109.4	C15—C16—H16C	109.5
N1—C6—O2	123.1 (3)	H16A—C16—H16C	109.5
N1—C6—C7	128.7 (3)	H16B—C16—H16C	109.5
O2—C6—C7	108.2 (3)	O10—C17—O11	125.6 (3)
C6—C7—Cl3	107.9 (2)	O10—C17—C5	126.3 (3)
C6—C7—Cl2	111.2 (3)	O11—C17—C5	108.1 (3)
Cl3—C7—Cl2	109.31 (19)	O11—C18—H18A	109.5
C6—C7—Cl1	109.7 (2)	O11—C18—H18B	109.5
Cl3—C7—Cl1	110.4 (2)	H18A—C18—H18B	109.5
Cl2—C7—Cl1	108.34 (16)	O11—C18—H18C	109.5
O4—C8—O3	122.4 (3)	H18A—C18—H18C	109.5
O4—C8—C9	126.3 (4)	H18B—C18—H18C	109.5
O3—C8—C9	111.2 (3)
C5—O1—C1—O2	−68.1 (3)	C3—C4—C5—C17	171.0 (3)
C5—O1—C1—C2	51.8 (3)	C1—O2—C6—N1	4.3 (5)
C6—O2—C1—O1	−94.0 (3)	C1—O2—C6—C7	−176.8 (2)
C6—O2—C1—C2	141.3 (3)	N1—C6—C7—Cl3	108.7 (4)
C8—O3—C2—C3	−151.7 (3)	O2—C6—C7—Cl3	−70.2 (3)
C8—O3—C2—C1	86.4 (3)	N1—C6—C7—Cl2	−11.1 (5)
O1—C1—C2—O3	72.9 (3)	O2—C6—C7—Cl2	170.0 (2)
O2—C1—C2—O3	−164.5 (2)	N1—C6—C7—Cl1	−131.0 (3)
O1—C1—C2—C3	−44.6 (3)	O2—C6—C7—Cl1	50.2 (3)
O2—C1—C2—C3	78.1 (3)	C2—O3—C8—O4	2.0 (5)
C10—O5—C3—C2	−93.1 (3)	C2—O3—C8—C9	−177.9 (3)
C10—O5—C3—C4	145.6 (3)	C3—O5—C10—O6	−3.6 (5)
O3—C2—C3—O5	167.4 (2)	C3—O5—C10—C11	178.4 (3)
C1—C2—C3—O5	−74.3 (3)	C4—O7—C12—O8	6.8 (5)
O3—C2—C3—C4	−75.9 (3)	C4—O7—C12—C13	−168.6 (3)
C1—C2—C3—C4	42.4 (3)	O8—C12—C13—C14	152.1 (4)
C12—O7—C4—C5	−159.4 (3)	O7—C12—C13—C14	−32.6 (4)
C12—O7—C4—C3	80.8 (3)	C12—C13—C14—C15	−61.0 (4)
O5—C3—C4—O7	−172.2 (2)	C13—C14—C15—O9	−9.9 (5)
C2—C3—C4—O7	69.0 (3)	C13—C14—C15—C16	168.3 (3)
O5—C3—C4—C5	72.1 (3)	C18—O11—C17—O10	2.6 (5)
C2—C3—C4—C5	−46.6 (3)	C18—O11—C17—C5	−176.6 (3)
C1—O1—C5—C4	−55.9 (3)	O1—C5—C17—O10	−6.6 (4)
C1—O1—C5—C17	−175.8 (2)	C4—C5—C17—O10	−128.3 (4)
O7—C4—C5—O1	−65.1 (3)	O1—C5—C17—O11	172.7 (2)
C3—C4—C5—O1	52.4 (3)	C4—C5—C17—O11	50.9 (3)
O7—C4—C5—C17	53.6 (3)