6-O-Cyano­meth­yl-1,2:3,4-di-O-isopropyl­idene-α-D-galactopyran­ose

The analysis of the title compound, C₁₄H₂₁NO₆, revealed a highly distorted conformation of the six-membered pyran­ose ring. The presence of two five-membered 1,3-dioxolane rings fused to the pyran­ose ring at the 1,2- and 3,4-positions is responsible for the severe deviation from the usual chair conformation of the pyran­ose ring. The three-dimensional packing is stabilized by weak hydrogen bonds of the C—H...O type.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.038
• wR factor = 0.092
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT063_ALERT_3_B Crystal Probably too Large for Beam Size .......       0.92 mm

Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.09 Ratio
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         33
            O6  -C7  -C8  -N1     86.00 16.00   1.555   1.555   1.555   1.555

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           32.98
           From the CIF: _reflns_number_total               3210
           Count of symmetry unique reflns         3296
           Completeness (_total/calc)             97.39%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: SHELXTL.

6-O-Cyanomethyl-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose

Crystal data

C14H21NO6	F(000) = 640
Mr = 299.32	Dx = 1.302 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5866 reflections
a = 5.4596 (1) Å	θ = 1.7–33.0°
b = 15.9758 (3) Å	µ = 0.10 mm^−1
c = 17.5111 (3) Å	T = 173 K
V = 1527.34 (5) Å^3	Needle, colourless
Z = 4	0.92 × 0.12 × 0.09 mm

Data collection

Siemens SMART CCD area-detector diffractometer	3210 independent reflections
Radiation source: fine-focus sealed tube	2609 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
ω scans	θmax = 33.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −8→8
Tmin = 0.912, Tmax = 0.991	k = −24→24
26365 measured reflections	l = −26→26

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	Only H-atom displacement parameters refined
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0453P)^2 + 0.1721P] where P = (Fo^2 + 2Fc^2)/3
3210 reflections	(Δ/σ)max < 0.001
215 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

Experimental. Data were collected at low temperature using a Siemens SMART CCD diffractometer equiped with a LT-2 device. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal–to–detector distance of 3.97 cm, 20 s per frame. Preliminary orientation matrix was obtained from the first 100 frames using SMART (Siemens, 1995). The collected frames were integrated using the preliminary orientation matrix which was updated every 100 frames. Final cell parameters were obtained by refinement on the position of 5866 reflections with I>10σ(I) after integration of all the frames data using SAINT (Siemens, 1995).

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	1.0114 (2)	0.61329 (6)	0.10359 (6)	0.0263 (2)
O2	0.7426 (2)	0.51515 (6)	0.06227 (6)	0.0295 (2)
O3	0.9780 (2)	0.35577 (6)	0.18812 (6)	0.0266 (2)
O4	0.7633 (2)	0.40210 (6)	0.29030 (6)	0.0297 (3)
O5	1.0300 (2)	0.54717 (6)	0.22123 (5)	0.0252 (2)
O6	0.7829 (2)	0.65878 (6)	0.32315 (6)	0.0292 (2)
N1	1.1767 (4)	0.65646 (14)	0.47331 (11)	0.0587 (5)
C1	1.0766 (3)	0.53896 (9)	0.14256 (7)	0.0242 (3)
H1	1.2550	0.5277	0.1346	0.022 (4)*
C2	0.9259 (3)	0.47007 (9)	0.10314 (8)	0.0263 (3)
H2	1.0315	0.4380	0.0668	0.033 (5)*
C3	0.7973 (3)	0.41064 (9)	0.15714 (8)	0.0252 (3)
H3	0.6700	0.3778	0.1291	0.034 (5)*
C4	0.6835 (3)	0.45278 (8)	0.22816 (8)	0.0241 (3)
H4	0.5007	0.4521	0.2246	0.027 (5)*
C5	0.7753 (3)	0.54206 (8)	0.23920 (8)	0.0227 (3)
H5	0.6817	0.5805	0.2048	0.025 (4)*
C6	0.7439 (4)	0.57038 (8)	0.32120 (8)	0.0274 (3)
H6A	0.5770	0.5568	0.3395	0.029 (5)*
H6B	0.8640	0.5417	0.3545	0.033 (5)*
C7	0.7769 (3)	0.69201 (10)	0.39770 (9)	0.0308 (3)
H7A	0.6331	0.6693	0.4252	0.039 (6)*
H7B	0.7585	0.7536	0.3949	0.048 (6)*
C8	1.0018 (4)	0.67146 (11)	0.44059 (10)	0.0374 (4)
C9	0.8520 (3)	0.59311 (9)	0.04130 (8)	0.0262 (3)
C10	0.9996 (4)	0.58472 (11)	−0.03171 (8)	0.0372 (4)
H10A	1.1205	0.5399	−0.0258	0.038 (6)*
H10B	1.0841	0.6376	−0.0423	0.050 (6)*
H10C	0.8896	0.5713	−0.0742	0.042 (6)*
C11	0.6542 (4)	0.65830 (11)	0.03582 (11)	0.0401 (4)
H11A	0.5362	0.6420	−0.0036	0.061 (7)*
H11B	0.7273	0.7124	0.0225	0.057 (7)*
H11C	0.5701	0.6630	0.0851	0.068 (8)*
C12	0.8899 (3)	0.33024 (9)	0.26145 (8)	0.0235 (3)
C13	0.7160 (3)	0.25676 (9)	0.25382 (10)	0.0324 (3)
H13A	0.6505	0.2422	0.3042	0.042 (6)*
H13B	0.8041	0.2086	0.2326	0.033 (5)*
H13C	0.5809	0.2720	0.2197	0.039 (5)*
C14	1.1035 (3)	0.31174 (11)	0.31225 (9)	0.0333 (3)
H14A	1.2130	0.3603	0.3136	0.051 (6)*
H14B	1.1926	0.2631	0.2925	0.053 (7)*
H14C	1.0447	0.2997	0.3640	0.040 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0349 (6)	0.0229 (5)	0.0211 (4)	−0.0044 (5)	−0.0059 (5)	0.0012 (4)
O2	0.0368 (6)	0.0250 (5)	0.0266 (5)	−0.0073 (5)	−0.0097 (5)	0.0055 (4)
O3	0.0359 (6)	0.0222 (5)	0.0217 (4)	0.0045 (5)	0.0051 (5)	0.0029 (4)
O4	0.0461 (7)	0.0211 (5)	0.0220 (4)	0.0071 (5)	0.0058 (5)	0.0030 (4)
O5	0.0274 (6)	0.0302 (5)	0.0179 (4)	−0.0024 (4)	−0.0022 (4)	−0.0006 (4)
O6	0.0448 (7)	0.0202 (4)	0.0225 (5)	0.0001 (5)	0.0021 (5)	−0.0026 (4)
N1	0.0565 (12)	0.0693 (13)	0.0503 (10)	0.0006 (11)	−0.0169 (10)	−0.0095 (9)
C1	0.0271 (7)	0.0264 (7)	0.0190 (6)	0.0003 (6)	−0.0007 (5)	0.0009 (5)
C2	0.0369 (9)	0.0226 (6)	0.0195 (6)	−0.0003 (6)	−0.0013 (6)	0.0006 (5)
C3	0.0359 (9)	0.0189 (6)	0.0208 (6)	−0.0001 (6)	−0.0022 (6)	0.0007 (5)
C4	0.0286 (7)	0.0201 (6)	0.0234 (6)	0.0002 (5)	0.0002 (6)	0.0016 (5)
C5	0.0268 (7)	0.0207 (6)	0.0206 (6)	0.0009 (6)	−0.0002 (5)	0.0003 (5)
C6	0.0394 (9)	0.0207 (6)	0.0222 (6)	−0.0004 (6)	0.0049 (7)	−0.0007 (5)
C7	0.0380 (9)	0.0281 (7)	0.0262 (7)	0.0003 (7)	0.0036 (7)	−0.0064 (6)
C8	0.0441 (10)	0.0397 (9)	0.0285 (7)	−0.0044 (9)	0.0007 (8)	−0.0064 (7)
C9	0.0334 (8)	0.0225 (6)	0.0227 (6)	−0.0047 (6)	−0.0063 (6)	0.0031 (5)
C10	0.0575 (12)	0.0334 (8)	0.0207 (6)	−0.0069 (9)	0.0011 (8)	0.0015 (6)
C11	0.0399 (10)	0.0328 (9)	0.0476 (10)	0.0013 (8)	−0.0094 (9)	0.0094 (8)
C12	0.0273 (7)	0.0210 (6)	0.0223 (6)	0.0023 (6)	0.0037 (6)	0.0016 (5)
C13	0.0314 (8)	0.0244 (7)	0.0413 (8)	−0.0022 (6)	0.0038 (7)	0.0022 (6)
C14	0.0320 (8)	0.0392 (8)	0.0289 (7)	0.0014 (7)	−0.0023 (7)	0.0054 (6)

Geometric parameters (Å, º)

O1—C1	1.4152 (17)	C5—H5	1.0000
O1—C9	1.4321 (18)	C6—H6A	0.9900
O2—C9	1.4293 (18)	C6—H6B	0.9900
O2—C2	1.4258 (19)	C7—C8	1.476 (3)
O3—C3	1.4266 (19)	C7—H7A	0.9900
O3—C12	1.4307 (17)	C7—H7B	0.9900
O4—C12	1.4321 (17)	C9—C10	1.517 (2)
O4—C4	1.4245 (17)	C9—C11	1.503 (2)
O5—C1	1.4070 (16)	C10—H10A	0.9800
O5—C5	1.4281 (19)	C10—H10B	0.9800
O6—C7	1.4097 (17)	C10—H10C	0.9800
O6—C6	1.4285 (16)	C11—H11A	0.9800
N1—C8	1.139 (3)	C11—H11B	0.9800
C1—C2	1.538 (2)	C11—H11C	0.9800
C1—H1	1.0000	C12—C14	1.496 (2)
C2—C3	1.513 (2)	C12—C13	1.516 (2)
C2—H2	1.0000	C13—H13A	0.9800
C3—C4	1.545 (2)	C13—H13B	0.9800
C3—H3	1.0000	C13—H13C	0.9800
C4—C5	1.5241 (19)	C14—H14A	0.9800
C4—H4	1.0000	C14—H14B	0.9800
C5—C6	1.5152 (19)	C14—H14C	0.9800
C1—O1—C9	109.36 (11)	O6—C7—H7A	109.3
C9—O2—C2	106.01 (12)	C8—C7—H7A	109.3
C3—O3—C12	106.51 (11)	O6—C7—H7B	109.3
C12—O4—C4	109.49 (10)	C8—C7—H7B	109.3
C1—O5—C5	112.75 (11)	H7A—C7—H7B	108.0
C7—O6—C6	113.01 (11)	N1—C8—C7	179.2 (2)
O1—C1—O5	110.39 (11)	O2—C9—O1	104.73 (11)
O1—C1—C2	104.43 (11)	O2—C9—C10	111.20 (12)
O5—C1—C2	114.16 (12)	O1—C9—C10	109.81 (14)
O1—C1—H1	109.2	O2—C9—C11	108.65 (14)
O5—C1—H1	109.2	O1—C9—C11	109.21 (13)
C2—C1—H1	109.2	C10—C9—C11	112.90 (14)
O2—C2—C3	107.76 (13)	C9—C10—H10A	109.5
O2—C2—C1	103.85 (11)	C9—C10—H10B	109.5
C3—C2—C1	114.64 (12)	H10A—C10—H10B	109.5
O2—C2—H2	110.1	C9—C10—H10C	109.5
C3—C2—H2	110.1	H10A—C10—H10C	109.5
C1—C2—H2	110.1	H10B—C10—H10C	109.5
O3—C3—C2	107.61 (14)	C9—C11—H11A	109.5
O3—C3—C4	103.86 (11)	C9—C11—H11B	109.5
C2—C3—C4	114.61 (12)	H11A—C11—H11B	109.5
O3—C3—H3	110.2	C9—C11—H11C	109.5
C2—C3—H3	110.2	H11A—C11—H11C	109.5
C4—C3—H3	110.2	H11B—C11—H11C	109.5
O4—C4—C5	109.54 (12)	O4—C12—O3	104.49 (10)
O4—C4—C3	104.14 (11)	O4—C12—C14	108.94 (13)
C5—C4—C3	112.19 (12)	O3—C12—C14	109.14 (13)
O4—C4—H4	110.3	O4—C12—C13	110.47 (13)
C5—C4—H4	110.3	O3—C12—C13	110.63 (12)
C3—C4—H4	110.3	C14—C12—C13	112.82 (13)
O5—C5—C6	107.56 (13)	C12—C13—H13A	109.5
O5—C5—C4	110.22 (12)	C12—C13—H13B	109.5
C6—C5—C4	111.25 (12)	H13A—C13—H13B	109.5
O5—C5—H5	109.3	C12—C13—H13C	109.5
C6—C5—H5	109.3	H13A—C13—H13C	109.5
C4—C5—H5	109.3	H13B—C13—H13C	109.5
O6—C6—C5	107.51 (11)	C12—C14—H14A	109.5
O6—C6—H6A	110.2	C12—C14—H14B	109.5
C5—C6—H6A	110.2	H14A—C14—H14B	109.5
O6—C6—H6B	110.2	C12—C14—H14C	109.5
C5—C6—H6B	110.2	H14A—C14—H14C	109.5
H6A—C6—H6B	108.5	H14B—C14—H14C	109.5
O6—C7—C8	111.60 (14)
C9—O1—C1—O5	−127.74 (13)	C1—O5—C5—C4	70.74 (14)
C9—O1—C1—C2	−4.60 (16)	O4—C4—C5—O5	76.09 (15)
C5—O5—C1—O1	74.87 (15)	C3—C4—C5—O5	−39.05 (16)
C5—O5—C1—C2	−42.41 (16)	O4—C4—C5—C6	−43.13 (18)
C9—O2—C2—C3	153.24 (11)	C3—C4—C5—C6	−158.27 (14)
C9—O2—C2—C1	31.25 (14)	C7—O6—C6—C5	−175.51 (14)
O1—C1—C2—O2	−16.32 (15)	O5—C5—C6—O6	71.60 (16)
O5—C1—C2—O2	104.33 (13)	C4—C5—C6—O6	−167.61 (13)
O1—C1—C2—C3	−133.62 (13)	C6—O6—C7—C8	74.57 (19)
O5—C1—C2—C3	−12.98 (19)	O6—C7—C8—N1	86 (16)
C12—O3—C3—C2	152.43 (11)	C2—O2—C9—O1	−34.59 (15)
C12—O3—C3—C4	30.54 (14)	C2—O2—C9—C10	83.95 (15)
O2—C2—C3—O3	170.14 (11)	C2—O2—C9—C11	−151.20 (13)
C1—C2—C3—O3	−74.81 (15)	C1—O1—C9—O2	23.91 (16)
O2—C2—C3—C4	−74.91 (16)	C1—O1—C9—C10	−95.57 (14)
C1—C2—C3—C4	40.15 (19)	C1—O1—C9—C11	140.14 (14)
C12—O4—C4—C5	−126.21 (13)	C4—O4—C12—O3	24.82 (15)
C12—O4—C4—C3	−6.03 (15)	C4—O4—C12—C14	141.36 (13)
O3—C3—C4—O4	−14.94 (15)	C4—O4—C12—C13	−94.19 (14)
C2—C3—C4—O4	−132.05 (14)	C3—O3—C12—O4	−34.71 (14)
O3—C3—C4—C5	103.45 (13)	C3—O3—C12—C14	−151.11 (12)
C2—C3—C4—C5	−13.67 (19)	C3—O3—C12—C13	84.19 (14)
C1—O5—C5—C6	−167.82 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10C···O4^i	0.98	2.55	3.438 (2)	150
C13—H13B···O6^ii	0.98	2.58	3.428 (2)	144

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