2-N-Benzyl-2,6-dide-oxy-2,6-imino-3,4-O-iso-propyl-idene-d-allono-nitrile.

X-ray crystallography firmly established the relative stereochemistry of the title compound, C16H20N2O3. The acetonide ring adopts an envelope conformation with one of the O atoms as the flap and the piperidine ring adopts a slightly twisted boat conformation. The absolute configuration was determined by use of d-ribose as the starting material. The compound exists as O-H⋯O hydrogen-bonded chains of mol-ecules running parallel to the b axis.

Related literature

For the biological activity of polyhy­droxy­lated piperidines, see: Nash et al. (2011 ▶); Watson et al. (2001 ▶). For a related α-imino­nitrile, see: Ayers et al. (2012 ▶). For the hydrogen-atom treatment, see; Cooper et al. (2010 ▶). For details of the low temperature equipment used in the experiment, see: Cosier & Glazer (1986 ▶). For the weighting scheme, see: Prince (1982 ▶); Watkin (1994 ▶).

Experimental

Crystal data

C16H20N2O3

M = 288.35

Orthorhombic,

a = 8.3978 (3) Å

b = 11.2689 (4) Å

c = 15.9210 (6) Å

V = 1506.67 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 150 K

0.4 × 0.4 × 0.2 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ▶) T min = 0.91, T max = 0.98

11529 measured reflections

1970 independent reflections

1422 reflections with I > 2.0σ(I)

R int = 0.079

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.121

S = 0.95

1970 reflections

190 parameters

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.42 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 datablock(s) I, global. DOI: 10.1107/S1600536813030584/lh5665sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813030584/lh5665Isup2.hkl

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

C16H20N2O3	F(000) = 616
Mr = 288.35	Dx = 1.271 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1934 reflections
a = 8.3978 (3) Å	θ = 5–27°
b = 11.2689 (4) Å	µ = 0.09 mm−1
c = 15.9210 (6) Å	T = 150 K
V = 1506.67 (9) Å3	Plate, colourless
Z = 4	0.4 × 0.4 × 0.2 mm

Nonius KappaCCD diffractometer	1422 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.079
ω scans	θmax = 27.5°, θmin = 5.1°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −10→10
Tmin = 0.91, Tmax = 0.98	k = −14→14
11529 measured reflections	l = −20→20
1970 independent reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044	H-atom parameters constrained
wR(F2) = 0.121	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: 9.51 13.9 7.19 2.01
S = 0.95	(Δ/σ)max = 0.0000939
1970 reflections	Δρmax = 0.47 e Å−3
190 parameters	Δρmin = −0.42 e Å−3
0 restraints

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1 K.

	x	y	z	Uiso*/Ueq
O1	0.6465 (3)	0.06340 (19)	0.37776 (14)	0.0305
C2	0.5963 (4)	0.1832 (3)	0.37195 (18)	0.0259
C3	0.6544 (4)	0.2450 (3)	0.29350 (18)	0.0245
O4	0.5816 (3)	0.19584 (18)	0.21979 (12)	0.0272
C5	0.5779 (4)	0.2890 (3)	0.15876 (18)	0.0261
O6	0.5489 (3)	0.39518 (18)	0.20739 (13)	0.0271
C7	0.6006 (4)	0.3759 (3)	0.29150 (18)	0.0256
C8	0.4595 (4)	0.4018 (3)	0.35050 (19)	0.0263
N9	0.3478 (3)	0.3035 (2)	0.34958 (16)	0.0261
C10	0.4160 (4)	0.1919 (3)	0.38247 (19)	0.0270
C11	0.1968 (4)	0.3292 (3)	0.3920 (2)	0.0318
C12	0.1021 (4)	0.4285 (3)	0.35313 (19)	0.0274
C13	0.0911 (5)	0.4450 (3)	0.26682 (19)	0.0315
C14	−0.0032 (5)	0.5344 (3)	0.23328 (19)	0.0323
C15	−0.0876 (4)	0.6088 (3)	0.2858 (2)	0.0308
C16	−0.0756 (5)	0.5947 (3)	0.3724 (2)	0.0343
C17	0.0182 (4)	0.5058 (3)	0.4056 (2)	0.0292
C18	0.5178 (5)	0.4307 (3)	0.4370 (2)	0.0328
N19	0.5612 (5)	0.4487 (3)	0.50421 (18)	0.0470
C20	0.4377 (4)	0.2689 (3)	0.1017 (2)	0.0328
C21	0.7352 (5)	0.3002 (4)	0.1127 (2)	0.0385
H21	0.6469	0.2260	0.4201	0.0308*
H31	0.7717	0.2399	0.2892	0.0303*
H71	0.6919	0.4291	0.3037	0.0311*
H81	0.4052	0.4724	0.3289	0.0310*
H101	0.3912	0.1842	0.4427	0.0319*
H102	0.3691	0.1265	0.3501	0.0317*
H111	0.2187	0.3478	0.4519	0.0382*
H112	0.1318	0.2571	0.3895	0.0380*
H131	0.1502	0.3963	0.2302	0.0381*
H141	−0.0094	0.5442	0.1754	0.0379*
H151	−0.1536	0.6691	0.2632	0.0372*
H161	−0.1325	0.6461	0.4082	0.0410*
H171	0.0255	0.4957	0.4642	0.0353*
H201	0.4276	0.3351	0.0634	0.0489*
H202	0.3408	0.2637	0.1346	0.0490*
H203	0.4527	0.1972	0.0698	0.0487*
H212	0.7322	0.3683	0.0748	0.0564*
H213	0.8215	0.3108	0.1527	0.0572*
H211	0.7541	0.2275	0.0804	0.0572*
H11	0.5995	0.0236	0.3393	0.0472*

	U11	U22	U33	U12	U13	U23
O1	0.0390 (13)	0.0236 (11)	0.0289 (11)	0.0062 (10)	−0.0064 (10)	0.0008 (9)
C2	0.0334 (17)	0.0206 (14)	0.0237 (14)	0.0016 (14)	−0.0040 (13)	0.0000 (12)
C3	0.0305 (15)	0.0222 (13)	0.0208 (13)	0.0006 (14)	−0.0048 (14)	0.0002 (12)
O4	0.0383 (13)	0.0206 (9)	0.0227 (10)	−0.0004 (11)	−0.0020 (10)	0.0007 (9)
C5	0.0354 (17)	0.0203 (13)	0.0225 (14)	−0.0022 (14)	0.0008 (14)	0.0010 (12)
O6	0.0408 (13)	0.0194 (9)	0.0210 (10)	−0.0008 (10)	−0.0012 (10)	−0.0008 (8)
C7	0.0325 (16)	0.0229 (14)	0.0214 (14)	−0.0036 (13)	−0.0041 (14)	0.0010 (12)
C8	0.0354 (18)	0.0217 (14)	0.0218 (13)	−0.0011 (14)	−0.0012 (13)	0.0010 (12)
N9	0.0293 (13)	0.0201 (12)	0.0289 (12)	0.0013 (11)	0.0032 (12)	0.0036 (11)
C10	0.0359 (17)	0.0205 (14)	0.0247 (14)	0.0011 (14)	0.0014 (14)	0.0061 (12)
C11	0.0353 (19)	0.0314 (17)	0.0285 (16)	0.0043 (15)	0.0085 (15)	0.0053 (14)
C12	0.0306 (17)	0.0264 (15)	0.0253 (14)	−0.0003 (14)	0.0030 (13)	0.0033 (13)
C13	0.0408 (19)	0.0280 (15)	0.0257 (14)	0.0045 (16)	0.0066 (15)	0.0009 (13)
C14	0.042 (2)	0.0315 (16)	0.0236 (15)	−0.0002 (16)	−0.0002 (15)	0.0040 (13)
C15	0.0306 (17)	0.0283 (15)	0.0336 (16)	0.0003 (15)	−0.0043 (15)	0.0030 (14)
C16	0.0340 (19)	0.0366 (18)	0.0323 (16)	0.0076 (16)	−0.0012 (15)	−0.0040 (14)
C17	0.0304 (18)	0.0315 (17)	0.0258 (15)	0.0027 (14)	0.0001 (14)	−0.0024 (13)
C18	0.046 (2)	0.0235 (15)	0.0292 (16)	0.0004 (16)	0.0010 (15)	−0.0013 (13)
N19	0.072 (3)	0.0403 (17)	0.0285 (15)	−0.0022 (19)	−0.0039 (16)	−0.0078 (13)
C20	0.0394 (19)	0.0299 (17)	0.0289 (16)	−0.0040 (15)	−0.0061 (16)	0.0013 (13)
C21	0.040 (2)	0.0405 (19)	0.0349 (19)	0.0005 (18)	0.0091 (16)	0.0004 (18)

O1—C2	1.418 (4)	C11—C12	1.506 (5)
O1—H11	0.855	C11—H111	0.993
C2—C3	1.511 (4)	C11—H112	0.980
C2—C10	1.527 (5)	C12—C13	1.390 (4)
C2—H21	1.000	C12—C17	1.397 (4)
C3—O4	1.434 (4)	C13—C14	1.388 (5)
C3—C7	1.543 (4)	C13—H131	0.942
C3—H31	0.990	C14—C15	1.381 (5)
O4—C5	1.431 (3)	C14—H141	0.929
C5—O6	1.446 (4)	C15—C16	1.392 (5)
C5—C20	1.504 (5)	C15—H151	0.948
C5—C21	1.516 (5)	C16—C17	1.379 (5)
O6—C7	1.424 (3)	C16—H161	0.943
C7—C8	1.540 (5)	C17—H171	0.943
C7—H71	0.992	C18—N19	1.148 (4)
C8—N9	1.452 (4)	C20—H201	0.968
C8—C18	1.498 (4)	C20—H202	0.970
C8—H81	0.980	C20—H203	0.963
N9—C10	1.477 (4)	C21—H212	0.976
N9—C11	1.466 (4)	C21—H213	0.972
C10—H101	0.986	C21—H211	0.981
C10—H102	0.982
C2—O1—H11	108.4	N9—C10—H102	107.3
O1—C2—C3	113.4 (3)	H101—C10—H102	111.1
O1—C2—C10	110.4 (3)	N9—C11—C12	114.5 (3)
C3—C2—C10	112.4 (3)	N9—C11—H111	108.9
O1—C2—H21	106.4	C12—C11—H111	109.6
C3—C2—H21	105.9	N9—C11—H112	107.4
C10—C2—H21	107.8	C12—C11—H112	107.8
C2—C3—O4	111.2 (2)	H111—C11—H112	108.5
C2—C3—C7	111.3 (3)	C11—C12—C13	122.8 (3)
O4—C3—C7	103.1 (2)	C11—C12—C17	118.9 (3)
C2—C3—H31	110.6	C13—C12—C17	118.3 (3)
O4—C3—H31	110.2	C12—C13—C14	121.0 (3)
C7—C3—H31	110.2	C12—C13—H131	119.9
C3—O4—C5	106.4 (2)	C14—C13—H131	119.1
O4—C5—O6	104.3 (2)	C13—C14—C15	120.0 (3)
O4—C5—C20	108.4 (3)	C13—C14—H141	120.0
O6—C5—C20	108.4 (3)	C15—C14—H141	120.0
O4—C5—C21	111.8 (3)	C14—C15—C16	119.6 (3)
O6—C5—C21	109.7 (3)	C14—C15—H151	120.3
C20—C5—C21	113.8 (3)	C16—C15—H151	120.1
C5—O6—C7	109.0 (2)	C15—C16—C17	120.3 (3)
C3—C7—O6	104.8 (2)	C15—C16—H161	119.4
C3—C7—C8	113.2 (3)	C17—C16—H161	120.3
O6—C7—C8	108.1 (3)	C12—C17—C16	120.8 (3)
C3—C7—H71	110.3	C12—C17—H171	118.9
O6—C7—H71	109.1	C16—C17—H171	120.3
C8—C7—H71	111.1	C8—C18—N19	177.4 (4)
C7—C8—N9	110.3 (2)	C5—C20—H201	109.5
C7—C8—C18	110.5 (3)	C5—C20—H202	109.9
N9—C8—C18	112.8 (3)	H201—C20—H202	108.3
C7—C8—H81	107.4	C5—C20—H203	110.1
N9—C8—H81	108.4	H201—C20—H203	109.0
C18—C8—H81	107.3	H202—C20—H203	110.1
C8—N9—C10	113.3 (3)	C5—C21—H212	110.0
C8—N9—C11	113.8 (3)	C5—C21—H213	110.1
C10—N9—C11	109.9 (2)	H212—C21—H213	109.1
C2—C10—N9	113.6 (3)	C5—C21—H211	109.0
C2—C10—H101	108.1	H212—C21—H211	109.6
N9—C10—H101	109.8	H213—C21—H211	109.0
C2—C10—H102	107.0

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11···O6i	0.86	2.05	2.850 (5)	156 (1)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H11⋯O6i	0.86	2.05	2.850 (5)	156 (1)

Symmetry code: (i) .