7-Azido-N,N-diethyl-4,5-O-isopropyl-idene-4-C-methyl-3,6-anhydro-7-de-oxy-d-glycero-d-manno-heptonamide.

The reaction of 5-azido-5-de-oxy-2,3-O-isopropyl-idene-2-C-methyl-d-ribose with N,N-diethyl-2-(dimethyl-sulfuranyl-idene)acetamide gave the title compound, C(15)H(26)N(4)O(5), as the major product arising from initial formation of an epoxide which was subsequently opened by intra-molecular attack of the free 4-hydroxyl group. X-ray crystallography confirmed the relative stereochemistry of the title compound and the absolute configuration was determined by the use of d-ribose as the starting material. The crystal structure contains chains of mol-ecules running parallel to the a axis, being linked by weak bifurcated O-H⋯(N,N) hydrogen bonds.

Related literature

For related literature see: Assiego et al. (2004 ▶); Pino-González et al. (2003 ▶, 2008 ▶); Valpuesta Fernández et al. (1990 ▶); Valpuesta et al. (1993 ▶); Görbitz (1999 ▶).

Experimental

Crystal data

C15H26N4O5

M = 342.40

Orthorhombic,

a = 8.64400 (10) Å

b = 13.4195 (2) Å

c = 15.9146 (3) Å

V = 1846.06 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 150 K

0.60 × 0.60 × 0.40 mm

Data collection

Area diffractometer

Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ▶) T min = 0.82, T max = 0.96

23123 measured reflections

2354 independent reflections

2077 reflections with I > 2σ(I)

R int = 0.077

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.129

S = 1.02

1992 reflections

217 parameters

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −0.20 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/S1600536808044279/lh2750sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808044279/lh2750Isup2.hkl

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

C15H26N4O5	F(000) = 736
Mr = 342.40	Dx = 1.232 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2356 reflections
a = 8.6440 (1) Å	θ = 5–27°
b = 13.4195 (2) Å	µ = 0.09 mm−1
c = 15.9146 (3) Å	T = 150 K
V = 1846.06 (5) Å3	Plate, colourless
Z = 4	0.60 × 0.60 × 0.40 mm

Area diffractometer	2077 reflections with I > 2σ(I)
graphite	Rint = 0.077
ω scans	θmax = 27.5°, θmin = 5.1°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −11→11
Tmin = 0.82, Tmax = 0.96	k = −17→17
23123 measured reflections	l = −20→20
2354 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)] = 0.049	H-atom parameters constrained
wR(F2) = 0.129	Method = Modified Sheldrick w = 1/[σ2(F2) + (0.1P)2 + 0.29P], where P = [max(Fo2,0) + 2Fc2]/3
S = 1.02	(Δ/σ)max = 0.0003
1992 reflections	Δρmax = 0.24 e Å−3
217 parameters	Δρmin = −0.20 e Å−3
0 restraints

	x	y	z	Uiso*/Ueq
O1	0.35653 (19)	0.34433 (12)	0.66423 (11)	0.0350
C2	0.3014 (3)	0.24404 (17)	0.66153 (15)	0.0332
C3	0.4224 (3)	0.18015 (18)	0.70965 (16)	0.0371
O4	0.3791 (2)	0.17151 (16)	0.79595 (11)	0.0446
C5	0.4967 (3)	0.2129 (2)	0.84827 (18)	0.0489
O6	0.5741 (3)	0.28402 (17)	0.79711 (13)	0.0567
C7	0.5654 (3)	0.2496 (2)	0.71213 (16)	0.0414
C8	0.5218 (3)	0.33863 (19)	0.65738 (15)	0.0359
C9	0.5726 (3)	0.32292 (19)	0.56645 (15)	0.0369
N10	0.5219 (3)	0.40493 (18)	0.51111 (14)	0.0432
N11	0.3807 (3)	0.40751 (17)	0.49594 (14)	0.0432
N12	0.2579 (3)	0.4190 (2)	0.47516 (19)	0.0629
C13	0.4212 (5)	0.2678 (3)	0.9201 (2)	0.0714
C14	0.6054 (4)	0.1311 (3)	0.8787 (2)	0.0650
C15	0.4486 (3)	0.0783 (2)	0.6708 (2)	0.0472
C16	0.1375 (3)	0.23817 (17)	0.69753 (16)	0.0343
O17	0.0763 (2)	0.14313 (12)	0.67786 (11)	0.0401
C18	0.0305 (3)	0.31779 (18)	0.65939 (15)	0.0334
O19	−0.0340 (2)	0.29828 (14)	0.59206 (12)	0.0424
N20	0.0093 (2)	0.40342 (15)	0.70067 (14)	0.0364
C21	−0.0987 (3)	0.47788 (19)	0.66655 (18)	0.0407
C22	−0.0208 (4)	0.5595 (3)	0.6178 (2)	0.0626
C23	0.0809 (3)	0.4266 (2)	0.78247 (16)	0.0430
C24	−0.0166 (4)	0.3904 (3)	0.85556 (18)	0.0562
H21	0.2943	0.2241	0.6020	0.0397*
H71	0.6551	0.2162	0.6930	0.0485*
H81	0.5759	0.3970	0.6784	0.0443*
H91	0.5284	0.2612	0.5394	0.0490*
H92	0.6863	0.3164	0.5677	0.0495*
H131	0.4998	0.2997	0.9504	0.1074*
H132	0.3617	0.2267	0.9575	0.1071*
H133	0.3543	0.3189	0.9005	0.1069*
H141	0.7116	0.1505	0.8701	0.1022*
H142	0.5918	0.1211	0.9387	0.1023*
H143	0.5851	0.0695	0.8476	0.1021*
H151	0.5319	0.0397	0.6952	0.0807*
H152	0.3501	0.0445	0.6815	0.0799*
H153	0.4686	0.0848	0.6104	0.0790*
H161	0.1438	0.2430	0.7599	0.0419*
H211	−0.1602	0.4457	0.6266	0.0494*
H212	−0.1637	0.5025	0.7098	0.0491*
H222	−0.1025	0.5966	0.5865	0.1080*
H221	0.0567	0.5295	0.5787	0.1079*
H223	0.0279	0.6004	0.6627	0.1076*
H232	0.1785	0.3960	0.7850	0.0507*
H231	0.0915	0.4974	0.7838	0.0496*
H243	0.0323	0.4135	0.9063	0.0898*
H242	−0.0188	0.3185	0.8585	0.0891*
H241	−0.1201	0.4187	0.8522	0.0890*
H171	0.0318	0.1201	0.6319	0.0671*

	U11	U22	U33	U12	U13	U23
O1	0.0338 (8)	0.0344 (8)	0.0368 (8)	−0.0019 (7)	0.0028 (7)	−0.0011 (7)
C2	0.0358 (12)	0.0336 (11)	0.0303 (10)	−0.0013 (9)	−0.0010 (9)	−0.0023 (9)
C3	0.0367 (12)	0.0413 (12)	0.0333 (11)	0.0024 (10)	0.0011 (10)	0.0029 (10)
O4	0.0404 (9)	0.0598 (11)	0.0336 (9)	0.0000 (9)	−0.0027 (8)	0.0075 (8)
C5	0.0477 (15)	0.0614 (17)	0.0376 (12)	0.0017 (13)	−0.0068 (12)	0.0052 (12)
O6	0.0642 (13)	0.0683 (13)	0.0375 (9)	−0.0153 (11)	−0.0124 (10)	0.0036 (9)
C7	0.0361 (12)	0.0505 (14)	0.0375 (12)	−0.0017 (12)	−0.0042 (10)	−0.0010 (11)
C8	0.0316 (11)	0.0403 (12)	0.0358 (11)	−0.0059 (10)	0.0019 (10)	−0.0031 (11)
C9	0.0333 (11)	0.0418 (12)	0.0357 (11)	−0.0024 (10)	0.0015 (10)	0.0000 (10)
N10	0.0422 (12)	0.0454 (12)	0.0421 (11)	−0.0054 (10)	0.0024 (10)	0.0055 (9)
N11	0.0482 (14)	0.0450 (12)	0.0365 (10)	0.0012 (10)	0.0022 (10)	0.0005 (9)
N12	0.0513 (16)	0.080 (2)	0.0577 (15)	0.0105 (15)	−0.0074 (13)	0.0077 (15)
C13	0.079 (2)	0.092 (3)	0.0433 (15)	0.010 (2)	−0.0073 (17)	−0.0083 (16)
C14	0.0592 (19)	0.077 (2)	0.0588 (18)	0.0085 (17)	−0.0179 (17)	0.0139 (17)
C15	0.0442 (14)	0.0386 (12)	0.0586 (16)	0.0043 (12)	0.0040 (13)	0.0010 (12)
C16	0.0347 (12)	0.0340 (11)	0.0342 (10)	−0.0023 (10)	−0.0002 (10)	−0.0002 (10)
O17	0.0411 (9)	0.0356 (8)	0.0437 (9)	−0.0075 (8)	−0.0057 (8)	0.0017 (7)
C18	0.0286 (10)	0.0371 (11)	0.0345 (11)	−0.0013 (9)	0.0011 (9)	0.0013 (9)
O19	0.0397 (10)	0.0462 (9)	0.0413 (9)	0.0055 (8)	−0.0070 (8)	−0.0070 (8)
N20	0.0348 (10)	0.0377 (10)	0.0366 (9)	0.0027 (8)	−0.0017 (8)	−0.0055 (8)
C21	0.0356 (12)	0.0413 (12)	0.0451 (13)	0.0055 (10)	−0.0023 (11)	−0.0043 (11)
C22	0.063 (2)	0.0606 (19)	0.0639 (19)	0.0157 (16)	0.0146 (17)	0.0167 (16)
C23	0.0496 (15)	0.0401 (12)	0.0393 (13)	0.0020 (12)	−0.0046 (12)	−0.0080 (11)
C24	0.070 (2)	0.0591 (17)	0.0393 (13)	0.0089 (16)	0.0069 (14)	−0.0047 (13)

O1—C2	1.429 (3)	C14—H142	0.972
O1—C8	1.435 (3)	C14—H143	0.979
C2—C3	1.554 (3)	C15—H151	0.968
C2—C16	1.530 (3)	C15—H152	0.979
C2—H21	0.986	C15—H153	0.982
C3—O4	1.428 (3)	C16—O17	1.415 (3)
C3—C7	1.548 (4)	C16—C18	1.538 (3)
C3—C15	1.517 (4)	C16—H161	0.997
O4—C5	1.427 (4)	O17—H171	0.882
C5—O6	1.422 (4)	C18—O19	1.236 (3)
C5—C13	1.509 (5)	C18—N20	1.336 (3)
C5—C14	1.524 (4)	N20—C21	1.471 (3)
O6—C7	1.431 (3)	N20—C23	1.475 (3)
C7—C8	1.526 (4)	C21—C22	1.501 (4)
C7—H71	0.946	C21—H211	0.934
C8—C9	1.527 (3)	C21—H212	0.947
C8—H81	0.972	C22—H222	0.998
C9—N10	1.476 (3)	C22—H221	0.999
C9—H91	1.009	C22—H223	0.994
C9—H92	0.987	C23—C24	1.516 (4)
N10—N11	1.245 (4)	C23—H232	0.940
N11—N12	1.122 (4)	C23—H231	0.955
C13—H131	0.936	C24—H243	0.962
C13—H132	0.960	C24—H242	0.967
C13—H133	0.950	C24—H241	0.973
C14—H141	0.964
C2—O1—C8	106.25 (18)	C5—C14—H142	109.8
O1—C2—C3	106.27 (19)	H141—C14—H142	107.0
O1—C2—C16	110.26 (19)	C5—C14—H143	109.7
C3—C2—C16	114.23 (19)	H141—C14—H143	109.0
O1—C2—H21	107.7	H142—C14—H143	111.0
C3—C2—H21	111.4	C3—C15—H151	115.5
C16—C2—H21	106.8	C3—C15—H152	102.5
C2—C3—O4	110.0 (2)	H151—C15—H152	109.3
C2—C3—C7	102.59 (19)	C3—C15—H153	110.2
O4—C3—C7	103.5 (2)	H151—C15—H153	108.0
C2—C3—C15	113.4 (2)	H152—C15—H153	111.4
O4—C3—C15	110.9 (2)	C2—C16—O17	108.00 (19)
C7—C3—C15	115.7 (2)	C2—C16—C18	111.91 (19)
C3—O4—C5	110.1 (2)	O17—C16—C18	108.32 (19)
O4—C5—O6	105.2 (2)	C2—C16—H161	108.6
O4—C5—C13	108.9 (3)	O17—C16—H161	107.5
O6—C5—C13	108.1 (3)	C18—C16—H161	112.4
O4—C5—C14	110.1 (3)	C16—O17—H171	131.5
O6—C5—C14	112.1 (3)	C16—C18—O19	117.8 (2)
C13—C5—C14	112.2 (3)	C16—C18—N20	119.1 (2)
C5—O6—C7	107.4 (2)	O19—C18—N20	123.1 (2)
C3—C7—O6	105.1 (2)	C18—N20—C21	119.3 (2)
C3—C7—C8	105.0 (2)	C18—N20—C23	123.9 (2)
O6—C7—C8	107.4 (2)	C21—N20—C23	116.7 (2)
C3—C7—H71	111.2	N20—C21—C22	113.7 (2)
O6—C7—H71	114.5	N20—C21—H211	107.4
C8—C7—H71	112.9	C22—C21—H211	104.0
C7—C8—O1	104.13 (19)	N20—C21—H212	110.2
C7—C8—C9	111.2 (2)	C22—C21—H212	112.8
O1—C8—C9	111.5 (2)	H211—C21—H212	108.5
C7—C8—H81	108.4	C21—C22—H222	107.7
O1—C8—H81	114.2	C21—C22—H221	109.2
C9—C8—H81	107.4	H222—C22—H221	111.3
C8—C9—N10	112.2 (2)	C21—C22—H223	102.8
C8—C9—H91	114.2	H222—C22—H223	112.6
N10—C9—H91	104.2	H221—C22—H223	112.7
C8—C9—H92	106.3	N20—C23—C24	112.1 (2)
N10—C9—H92	112.0	N20—C23—H232	108.8
H91—C9—H92	108.2	C24—C23—H232	109.1
C9—N10—N11	115.3 (2)	N20—C23—H231	105.7
N10—N11—N12	171.3 (3)	C24—C23—H231	110.8
C5—C13—H131	107.4	H232—C23—H231	110.3
C5—C13—H132	114.9	C23—C24—H243	107.2
H131—C13—H132	109.5	C23—C24—H242	111.6
C5—C13—H133	111.5	H243—C24—H242	106.8
H131—C13—H133	106.3	C23—C24—H241	110.1
H132—C13—H133	107.0	H243—C24—H241	109.0
C5—C14—H141	110.3	H242—C24—H241	112.0

D—H···A	D—H	H···A	D···A	D—H···A
C9—H91···O19i	1.01	2.30	3.140 (4)	140
C9—H92···O19ii	0.99	2.46	3.441 (4)	172
C23—H232···O1	0.94	2.56	3.231 (4)	129
C23—H231···O17iii	0.95	2.51	3.269 (4)	136
O17—H171···N10iv	0.88	2.30	3.112 (4)	152
O17—H171···N11iv	0.88	2.45	3.313 (4)	167

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O17—H171⋯N10i	0.88	2.30	3.112 (4)	152
O17—H171⋯N11i	0.88	2.45	3.313 (4)	167

Symmetry code: (i) .