2-Azido-3,4;6,7-di-O-isopropyl-idene-α-d-glycero-d-talo-heptopyran-ose.

In the title compound, C(13)H(21)N(3)O(6), the six-membered ring adopts a twist-boat conformation with the azide group in the bowsprit position. The azide group is disordered over two sets of sites in a 0.642 (10):0.358 (10) ratio. The crystal structure consists of O-H⋯O hydrogen-bonded trimer units. The absolute configuration was determined from the use of d-mannose as the starting material.

Related literature

For Izumoring techniques, see: Izumori (2002 ▶, 2006 ▶); Yoshihara et al. (2008 ▶); Gullapalli et al. (2010 ▶); Rao et al. (2008 ▶, 2009 ▶); Jones et al. (2008 ▶); Jenkinson et al. (2009 ▶). For the synthesis of homonojirimycins, see: Compain et al. (2009 ▶); Asano (2009 ▶); Watson et al. (2001 ▶) and for their isolation, see: Ikeda et al. (2000 ▶); Asano et al. (1998 ▶); Kite et al. (1988 ▶). For the synthesis of the azido­heptitol, see: Beacham et al. (1991 ▶); Bruce et al. (1990 ▶); Myerscough et al. (1992 ▶). For the weighting scheme, see: Prince (1982 ▶); Watkin (1994 ▶).

Experimental

Crystal data

C13H21N3O6

M = 315.33

Trigonal,

a = 16.8793 (2) Å

c = 15.1043 (3) Å

V = 3726.83 (10) Å3

Z = 9

Mo Kα radiation

μ = 0.10 mm−1

T = 150 K

0.70 × 0.50 × 0.30 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ▶) T min = 0.63, T max = 0.97

23870 measured reflections

1889 independent reflections

1770 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.070

S = 0.87

1889 reflections

227 parameters

43 restraints

H-atom parameters constrained

Δρmax = 0.16 e Å−3

Δρmin = −0.16 e Å−3

Data collection: COLLECT (Nonius, 2001 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: CAMERON (Watkin et al., 1996 ▶); software used to prepare material for publication: CRYSTALS.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810003995/lh2989sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810003995/lh2989Isup2.hkl

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

C13H21N3O6	Dx = 1.264 Mg m−3
Mr = 315.33	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 1885 reflections
Hall symbol: R 3	θ = 5–28°
a = 16.8793 (2) Å	µ = 0.10 mm−1
c = 15.1043 (3) Å	T = 150 K
V = 3726.83 (10) Å3	Plate, colourless
Z = 9	0.70 × 0.50 × 0.30 mm
F(000) = 1512

Nonius KappaCCD diffractometer	1770 reflections with I > 2σ(I)
graphite	Rint = 0.034
ω scans	θmax = 27.5°, θmin = 5.2°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −21→21
Tmin = 0.63, Tmax = 0.97	k = −21→21
23870 measured reflections	l = −19→19
1889 independent reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027	H-atom parameters constrained
wR(F2) = 0.070	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)2]2 Ai are: 35.7 56.9 32.2 12.2 2.39
S = 0.87	(Δ/σ)max = 0.0004
1889 reflections	Δρmax = 0.16 e Å−3
227 parameters	Δρmin = −0.16 e Å−3
43 restraints

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.73085 (8)	0.56052 (8)	0.60278 (11)	0.0388
C2	0.71163 (11)	0.63258 (11)	0.58727 (14)	0.0334
C3	0.60997 (11)	0.59051 (10)	0.56713 (13)	0.0348
O4	0.55748 (8)	0.55027 (8)	0.64559 (12)	0.0420
C5	0.49780 (12)	0.45418 (11)	0.63308 (14)	0.0398
O6	0.53523 (9)	0.43128 (8)	0.55852 (11)	0.0414
C7	0.57940 (12)	0.51014 (10)	0.50233 (14)	0.0370
C9	0.72913 (13)	0.51340 (12)	0.52439 (14)	0.0407
O10	0.81499 (10)	0.55590 (10)	0.48357 (13)	0.0511
C14	0.50399 (17)	0.40362 (15)	0.71240 (16)	0.0540
C15	0.40195 (14)	0.43489 (16)	0.61352 (17)	0.0544
C16	0.74277 (12)	0.69311 (12)	0.66864 (14)	0.0376
O17	0.72041 (8)	0.76403 (8)	0.65905 (12)	0.0420
C18	0.80336 (12)	0.84914 (11)	0.63848 (14)	0.0408
O19	0.87138 (8)	0.82461 (9)	0.62410 (12)	0.0457
C20	0.84636 (13)	0.74546 (14)	0.67731 (16)	0.0468
C21	0.79042 (17)	0.88864 (16)	0.55377 (18)	0.0588
C22	0.82716 (16)	0.91340 (13)	0.71627 (16)	0.0519
H21	0.7470	0.6687	0.5353	0.0391*
H31	0.5978	0.6378	0.5436	0.0413*
H71	0.5361	0.5093	0.4580	0.0446*
H91	0.7123	0.4508	0.5415	0.0490*
H141	0.4682	0.3379	0.7027	0.0810*
H142	0.4804	0.4199	0.7637	0.0803*
H143	0.5683	0.4214	0.7219	0.0805*
H152	0.3632	0.3698	0.6047	0.0812*
H153	0.3773	0.4541	0.6630	0.0797*
H151	0.4011	0.4664	0.5607	0.0801*
H161	0.7134	0.6569	0.7208	0.0440*
H201	0.8648	0.7629	0.7392	0.0552*
H202	0.8739	0.7101	0.6556	0.0567*
H212	0.8455	0.9466	0.5425	0.0887*
H213	0.7396	0.9001	0.5601	0.0886*
H211	0.7793	0.8473	0.5054	0.0875*
H222	0.8852	0.9682	0.7049	0.0781*
H223	0.8309	0.8835	0.7700	0.0772*
H221	0.7802	0.9302	0.7229	0.0777*
H101	0.8447	0.5336	0.5065	0.0762*
C80	0.66053 (13)	0.51225 (11)	0.45706 (13)	0.0399	0.642 (10)
N110	0.6365 (5)	0.4337 (5)	0.3965 (5)	0.0459	0.642 (10)
N120	0.6176 (3)	0.4422 (3)	0.3203 (3)	0.0485	0.642 (10)
N130	0.5963 (4)	0.4412 (3)	0.2497 (2)	0.0824	0.642 (10)
C81	0.66053 (13)	0.51225 (11)	0.45706 (13)	0.0399	0.358 (10)
N111	0.6151 (11)	0.4225 (12)	0.4122 (11)	0.0617	0.358 (10)
N121	0.6429 (6)	0.4295 (6)	0.3378 (7)	0.0510	0.358 (10)
N131	0.6661 (7)	0.4252 (6)	0.2652 (4)	0.0936	0.358 (10)
H801	0.6910	0.5680	0.4222	0.0469*	0.642 (10)
H811	0.6898	0.5645	0.4171	0.0473*	0.358 (10)

	U11	U22	U33	U12	U13	U23
O1	0.0408 (6)	0.0341 (6)	0.0477 (7)	0.0235 (5)	−0.0023 (5)	0.0055 (5)
C2	0.0319 (7)	0.0255 (7)	0.0436 (8)	0.0150 (6)	−0.0009 (6)	0.0042 (6)
C3	0.0331 (8)	0.0254 (7)	0.0461 (9)	0.0149 (6)	−0.0014 (6)	0.0017 (6)
O4	0.0358 (6)	0.0264 (6)	0.0545 (7)	0.0084 (5)	0.0071 (5)	−0.0027 (5)
C5	0.0368 (8)	0.0246 (7)	0.0493 (9)	0.0088 (6)	−0.0017 (7)	−0.0007 (6)
O6	0.0444 (7)	0.0234 (5)	0.0493 (7)	0.0117 (5)	−0.0005 (5)	0.0004 (5)
C7	0.0401 (8)	0.0251 (7)	0.0449 (9)	0.0156 (6)	−0.0042 (7)	0.0014 (6)
C9	0.0454 (9)	0.0324 (8)	0.0518 (10)	0.0251 (7)	0.0036 (8)	0.0077 (7)
O10	0.0522 (8)	0.0543 (8)	0.0632 (8)	0.0390 (7)	0.0123 (7)	0.0181 (7)
C14	0.0670 (13)	0.0407 (10)	0.0523 (12)	0.0254 (10)	−0.0002 (10)	0.0048 (8)
C15	0.0359 (9)	0.0534 (12)	0.0609 (13)	0.0125 (9)	−0.0035 (9)	−0.0009 (9)
C16	0.0341 (8)	0.0311 (7)	0.0438 (9)	0.0133 (7)	−0.0011 (6)	0.0024 (6)
O17	0.0318 (6)	0.0271 (5)	0.0606 (8)	0.0100 (5)	0.0033 (5)	−0.0025 (5)
C18	0.0361 (8)	0.0287 (8)	0.0475 (9)	0.0086 (7)	0.0026 (7)	0.0017 (7)
O19	0.0317 (6)	0.0391 (7)	0.0562 (8)	0.0100 (5)	0.0028 (5)	0.0012 (6)
C20	0.0368 (9)	0.0405 (9)	0.0573 (11)	0.0150 (8)	−0.0072 (8)	−0.0021 (8)
C21	0.0641 (13)	0.0517 (12)	0.0538 (11)	0.0239 (11)	−0.0022 (10)	0.0072 (9)
C22	0.0556 (12)	0.0312 (9)	0.0533 (11)	0.0099 (8)	0.0038 (9)	−0.0034 (8)
C80	0.0489 (10)	0.0299 (8)	0.0448 (9)	0.0226 (7)	−0.0012 (7)	−0.0005 (6)
N110	0.064 (4)	0.033 (3)	0.043 (3)	0.026 (3)	0.004 (3)	−0.0027 (19)
N120	0.049 (2)	0.0377 (17)	0.049 (2)	0.0148 (14)	0.0016 (15)	−0.0079 (14)
N130	0.104 (4)	0.063 (2)	0.052 (2)	0.021 (2)	−0.0091 (19)	−0.0184 (15)
C81	0.0489 (10)	0.0299 (8)	0.0448 (9)	0.0226 (7)	−0.0012 (7)	−0.0005 (6)
N111	0.072 (7)	0.034 (4)	0.060 (6)	0.013 (4)	0.032 (4)	0.001 (3)
N121	0.053 (4)	0.045 (3)	0.052 (4)	0.022 (3)	0.000 (3)	0.002 (3)
N131	0.112 (7)	0.094 (6)	0.050 (4)	0.033 (5)	0.009 (4)	−0.010 (3)

O1—C2	1.4261 (18)	C15—H152	0.966
O1—C9	1.419 (2)	C15—H153	0.985
C2—C3	1.524 (2)	C15—H151	0.963
C2—C16	1.515 (2)	C16—O17	1.431 (2)
C2—H21	0.991	C16—C20	1.520 (2)
C3—O4	1.431 (2)	C16—H161	0.968
C3—C7	1.538 (2)	O17—C18	1.452 (2)
C3—H31	0.986	C18—O19	1.419 (2)
O4—C5	1.4309 (19)	C18—C21	1.508 (3)
C5—O6	1.436 (2)	C18—C22	1.511 (3)
C5—C14	1.505 (3)	O19—C20	1.430 (2)
C5—C15	1.511 (3)	C20—H201	0.983
O6—C7	1.434 (2)	C20—H202	0.978
C7—H71	0.986	C21—H212	0.971
C7—C80	1.515 (3)	C21—H213	0.974
C7—H71	0.986	C21—H211	0.962
C7—C81	1.515 (3)	C22—H222	0.969
C9—O10	1.398 (2)	C22—H223	0.974
C9—H91	0.982	C22—H221	0.971
C9—C80	1.534 (3)	C80—N110	1.491 (8)
C9—O10	1.398 (2)	C80—H801	0.971
C9—H91	0.982	N110—N120	1.221 (8)
C9—C81	1.534 (3)	N120—N130	1.123 (6)
O10—H101	0.838	C81—N111	1.477 (19)
C14—H141	0.974	C81—H811	0.975
C14—H142	0.971	N111—N121	1.201 (16)
C14—H143	0.982	N121—N131	1.179 (13)
C2—O1—C9	113.04 (12)	C5—C15—H153	111.3
O1—C2—C3	108.58 (13)	H152—C15—H153	108.8
O1—C2—C16	106.97 (13)	C5—C15—H151	110.7
C3—C2—C16	113.98 (14)	H152—C15—H151	108.9
O1—C2—H21	109.4	H153—C15—H151	108.8
C3—C2—H21	108.7	C2—C16—O17	109.54 (13)
C16—C2—H21	109.2	C2—C16—C20	111.86 (16)
C2—C3—O4	109.97 (14)	O17—C16—C20	103.32 (14)
C2—C3—C7	109.94 (14)	C2—C16—H161	109.8
O4—C3—C7	104.67 (12)	O17—C16—H161	110.2
C2—C3—H31	109.7	C20—C16—H161	111.9
O4—C3—H31	110.6	C16—O17—C18	108.78 (13)
C7—C3—H31	111.8	O17—C18—O19	105.35 (14)
C3—O4—C5	110.27 (13)	O17—C18—C21	109.73 (16)
O4—C5—O6	104.70 (14)	O19—C18—C21	108.44 (17)
O4—C5—C14	109.19 (15)	O17—C18—C22	108.82 (15)
O6—C5—C14	107.89 (15)	O19—C18—C22	111.41 (16)
O4—C5—C15	109.94 (15)	C21—C18—C22	112.81 (17)
O6—C5—C15	110.88 (16)	C18—O19—C20	106.42 (14)
C14—C5—C15	113.82 (17)	C16—C20—O19	102.19 (15)
C5—O6—C7	107.99 (12)	C16—C20—H201	110.8
C3—C7—O6	103.40 (13)	O19—C20—H201	110.7
C3—C7—H71	111.3	C16—C20—H202	112.1
O6—C7—H71	110.5	O19—C20—H202	111.9
C3—C7—C80	111.47 (14)	H201—C20—H202	109.0
O6—C7—C80	109.47 (13)	C18—C21—H212	108.5
H71—C7—C80	110.5	C18—C21—H213	109.9
C3—C7—O6	103.40 (13)	H212—C21—H213	108.2
C3—C7—H71	111.3	C18—C21—H211	110.0
O6—C7—H71	110.5	H212—C21—H211	109.8
C3—C7—C81	111.47 (14)	H213—C21—H211	110.3
O6—C7—C81	109.47 (13)	C18—C22—H222	109.1
H71—C7—C81	110.5	C18—C22—H223	109.8
O1—C9—O10	110.79 (15)	H222—C22—H223	110.3
O1—C9—H91	107.3	C18—C22—H221	109.1
O10—C9—H91	109.7	H222—C22—H221	108.8
O1—C9—C80	111.36 (13)	H223—C22—H221	109.8
O10—C9—C80	107.23 (15)	C9—C80—C7	111.64 (15)
H91—C9—C80	110.5	C9—C80—N110	106.6 (3)
O1—C9—O10	110.79 (15)	C7—C80—N110	114.6 (3)
O1—C9—H91	107.3	C9—C80—H801	108.4
O10—C9—H91	109.7	C7—C80—H801	107.6
O1—C9—C81	111.36 (13)	N110—C80—H801	107.8
O10—C9—C81	107.23 (15)	C80—N110—N120	116.4 (6)
H91—C9—C81	110.5	N110—N120—N130	173.3 (6)
C9—O10—H101	106.7	C9—C81—C7	111.64 (15)
C5—C14—H141	110.3	C9—C81—N111	108.6 (8)
C5—C14—H142	108.7	C7—C81—N111	100.5 (5)
H141—C14—H142	109.5	C9—C81—H811	111.2
C5—C14—H143	108.9	C7—C81—H811	110.2
H141—C14—H143	109.4	N111—C81—H811	114.3
H142—C14—H143	110.1	C81—N111—N121	110.6 (11)
C5—C15—H152	108.4	N111—N121—N131	172.0 (13)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H153···O10i	0.99	2.51	3.361 (3)	145
O10—H101···O6ii	0.84	1.93	2.761 (3)	171
C80—H801···O4iii	0.97	2.36	3.296 (3)	161
C81—H801···O4iii	0.97	2.36	3.296 (3)	161
C80—H811···O4iii	0.97	2.34	3.296 (3)	166
C81—H811···O4iii	0.97	2.34	3.296 (3)	166

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H101⋯O6i	0.84	1.93	2.761 (3)	171

Symmetry code: (i) .