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Acta Cryst.(2002). E58, o65±o66 DOI: 10.1107/S1600536801019791 Ilia A. Guzeiet al. C17H16N2O6S

o65

organic papers

Acta Crystallographica Section E Structure Reports

Online

ISSN 1600-5368

(2

S

,3

S

)-2-Benzyl-3-(nosylamino)butano-4-lactone

Ilia A. Guzei,a* Joseph M. Langenhanband Yong Jun Chungb

a2124 Chemistry Department, University of

Wisconsin-Madison, 1101 University Ave, Madison, WI 53706, USA, andbChemistry Department, University of Wisconsin-Madison, 1101 University Ave, Madison, WI 53706, USA

Correspondence e-mail: iguzei@chem.wisc.edu

Key indicators

Single-crystal X-ray study

T= 173 K

Mean(C±C) = 0.003 AÊ

Rfactor = 0.029

wRfactor = 0.073

Data-to-parameter ratio = 11.1

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved

In the crystalline state, the title molecule, C17H16N2O6S, with

its ®ve-membered ring in an envelope conformation, produces a three-dimensional network of weak intermolecular hydro-gen-bonding interactions.

Comment

During our studies aimed at,-disubstituted -amino acids

possessing sheet-forming propensity, we isolated and structu-rally characterized (2S,3S )-2-benzyl-3-(nosylamino)butano-4-lactone, (I), where nosyl is 2-nitrophenylsulfonyl.

Compound (I) crystallizes in the chiral space groupP212121

as discrete molecules with theScon®guration about the two

chiral centers C7 and C10 (Fig. 1). The ®ve-membered heterocycle is in an envelope conformation, with C7 deviating from the C8/C9/C10/O5 plane by 0.409 (2) AÊ. The puckering amplitudeq2is 0.257 (2) AÊ, while the phase angle'2is 0.7 (4)

(Cremer & Pople, 1975); as expected, this corresponds to the

1Econformation. The nitro group at C1 is not coplanar with

the C1ÐC6 ring as the planar arrangement would bring atoms O1 and H2, as well as atoms O1 and O3, into close proximity, thereby inducing steric repulsion. The torsion angle O1Ð

N1ÐC1ÐC2 measures 50.8 (2).

There are weak intermolecular hydrogen-bonding inter-actions in the crystal of (I), resulting in a three-dimensional

network. These include NÐH O, CÐH O and CÐH

interactions (Table 2; CgAis the centroid of the C1ÐC6 ring

and CgBis the centroid of the C12ÐC17 ring). In addition, the centroids of rings C1ÐC6 and C12ÐC17 are separated by 3.807 (1) AÊ, resulting in intramolecular-stacking. The rings are almost parallel, with a dihedral angle between the ring planes of 13.03 (9).

The sum of the bond angles around N2 is 352.58 (13); thus

atom N2 is essentially in ansp2con®guration. A search of the

Cambridge Structural Database (Allen & Kennard, 1993) revealed 24 molecules with similar SÐN single bonds. The

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average bond length of 1.62 (2) AÊ somewhat exceeds the length of the SÐN2 bond in (I) [1.5987 (16) AÊ] which is likely

due to the increasedsp2character of atom N2.

Experimental

(2S,3S)-2±Benzyl-3-(nosylamino)butano-4-lactone was synthesized from (3S)-3-(nosylamino)butano-4-lactone according to the proce-dure developed by Jefford & Wang (1993) and Jefford & McNulty (1994). To a solution of hexamethyldisilazane (HMDS, 2.3 equiva-lents) andn-BuLi (2.3 equivalents) at 195 K, (3S )-3-(nosylamino)-butano-4-lactone was added. Benzyl bromide (2.1 equivalents) was added to the resultant dianion to afford a mixture of products which, after chromatography, provided (I) in a 42% yield.1H NMR (CDCl

3

+ DMSO, 296 K, p.p.m.):8.30 (s, 1 H), 7.95±7.92 (d, 1 H), 7.80±7.69 (m, 2 H), 7.14±7.02 (m, 5 H), 4.19±3.99 (ABofABX, 2H), 3.94±3.80 (XofABX, 1 H), 3.12 (m, 1 H), 3.00±2.97 (m, 2 H);13C NMR (CDCl

3

+ DMSO, 296 K, p.p.m.): 175.3, 136.3, 133.7, 133.4, 132.2, 130.3, 129.1, 128.2, 126.5, 124.6, 70.9, 52.8, 45.7, 32.7.

Crystal data

C17H16N2O6S

Mr= 376.38

Orthorhombic,P212121 a= 7.3711 (5) AÊ

b= 11.0756 (7) AÊ

c= 20.5014 (12) AÊ

V= 1673.72 (18) AÊ3 Z= 4

Dx= 1.494 Mg mÿ3

MoKradiation

Cell parameters from 5380 re¯ections

= 2.0±26.0

= 0.23 mmÿ1

T= 173 (2) K

Block, colorless

0.500.400.30 mm

Data collection

Bruker CCD-1000 diffractometer

!scans

Absorption correction: empirical (SADABS; Blessing, 1995)

Tmin= 0.893,Tmax= 0.934

7922 measured re¯ections 3312 independent re¯ections

3081 re¯ections withI> 2(I)

Rint= 0.023

max= 26.4

h=ÿ9!8

k=ÿ13!13

l=ÿ25!12

Re®nement

Re®nement onF2

R[F2> 2(F2)] = 0.029 wR(F2) = 0.073

S= 1.03

3312 re¯ections 299 parameters

All H-atom parameters re®ned

w= 1/[2(F

o2) + (0.045P)2

+ 0.1922P]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.001 max= 0.32 e AÊÿ3 min=ÿ0.27 e AÊÿ3

Absolute structure: Flack (1983) Flack parameter = 0.04 (6)

Table 1

Selected bond lengths (AÊ).

SÐO4 1.4277 (14)

SÐO3 1.4391 (13)

SÐN2 1.5987 (16)

SÐC6 1.7891 (17)

O1ÐN1 1.2218 (19)

O2ÐN1 1.2203 (19)

Table 2

Hydrogen-bonding geometry (AÊ,).

DÐH A DÐH H A D A DÐH A

N2ÐH2N O3i 0.78 (2) 2.19 (2) 2.917 (2) 154 (2)

C7ÐH7 O6ii 0.867 (19) 2.532 (19) 3.269 (2) 143.5 (16)

C2ÐH2 CgBiiii 0.93 (2) 2.66 (2) 3.4214 (18) 139.7 (17)

C14ÐH14 CgAiv 0.97 (2) 3.17 (2) 3.936 (2) 136.8 (18)

Symmetry codes: (i)1

2‡x;12ÿy;2ÿz; (ii)xÿ12;ÿ21ÿy;2ÿz; (iii) 1ÿx;12‡y;32ÿz;

(iv)ÿx;yÿ1 2;32ÿz.

H atoms were located from a difference map and both positional and isotropic displacement parameters were re®ned. For H atoms, the CÐH range is 0.87 (2)±1.03 (2) AÊ and the NÐH distance is 0.78 (2) AÊ.

Data collection:SMART(Bruker, 1997); cell re®nement:SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to re®ne structure:SHELXTL; molecular graphics:SHELXTL; software used to prepare material for publication: SHELXTL and PARST (Nardelli, 1983, 1995).

JML was supported by a National Science Foundation predoctoral fellowship.

References

Allen, F. H. & Kennard, O. (1993).Chem. Des. Autom. News,8, 1, 31±37.

Blessing, R. H. (1995).Acta Cryst.A51, 33±38.

Bruker (1997).SHELXTL, SMARTandSAINT. Bruker AXS Inc., Madison,

Wisconsin, USA.

Cremer, D. & Pople, J. A. (1975).J. Am. Chem. Soc.97, 1358±1367.

Flack, H. D. (1983).Acta Cryst.A39, 876±881.

Jefford, C. W. & McNulty, J. (1994).Helv. Chim. Acta,77, 2142±2146. Jefford, C. W. & Wang, J. (1993).Tetrahedron Lett.34, 1111±1114.

Nardelli, M. (1983).Comput. Chem.7, 95±98.

Nardelli, M. (1995).J. Appl. Cryst.28, 659.

Figure 1

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supporting information

sup-1

Acta Cryst. (2002). E58, o65–o66

supporting information

Acta Cryst. (2002). E58, o65–o66 [doi:10.1107/S1600536801019791]

(2

S

,3

S

)-2-Benzyl-3-(nosylamino)butano-4-lactone

Ilia A. Guzei, Joseph M. Langenhan and Yong Jun Chung

S1. Comment

During our studies toward α,β-disubstituted β-amino acids posessing sheet-forming propensity, we isolated and structurally characterized (2S,3S)-2-benzyl-3-(nosylamino)butano-4-lactone, (I).

Compound (I) crystallizes in the chiral space group P212121 as discrete molecules with the S configuration about the two

chiral centers C7 and C10. The five-membered heterocycle is in an envelope conformation, with C7 deviating from the C8/C9/C10/O5 plane by 0.409 (2) Å. The puckering amplitude q2 is 0.257 (2) Å, while the phase angle φ2 is 0.7 (4)°

(Cremer & Pople, 1975). Expectedly, the latter corresponds to the 1E conformation. The nitro group at C1 is not coplanar

with the C1—C6 ring as the planar arrangement would bring atoms O1 and H2, as well as atoms O1 and O3, into close proximity to induce steric repulsion. The torsion angle O1—N1—C1—C2 measures 50.8 (2)°.

There are weak intermolecular hydrogen bonding interactions in the crystal of (I) that form a three-dimensional network. These include N—H···O, C—H···O and C—H···π interactions (Table 2; CgA is the centroid of the C1—C6 ring

and CgB is the centroid of the C12—C17 ring). In addition, the centroids of rings C1—C6 and C12—C17 are within

3.807 (1) Å, resulting in intramolecualr π-stacking. The rings are almost parallel, with a dihedral angle between the ring planes of 13.03 (9)°.

Atom N2 is almost planar, with the sum of the bond angles about it amounting to 352.58 (13)°. Thus, atom N2 is essentially in an sp2 configuration. A search of the Cambridge Structural Database (Allen & Kennard, 1993) revealed 24

molecules with similar S—N single bonds. The average bond lrngth of 1.62 (2) Å somewhat exceeds the length of the S —N2 bond in (I) [1.5987 (16) Å] which is likely due to the increased sp2 character of atom N2.

S2. Experimental

(2S, 3S)-2-Benzyl-3-(nosylamino)butano-4-lactone was synthesized from (3S)-3-(nosylamino)butano-4-lactone according to the procedure developed by Jefford et al. (1993, 1994). To a solution of HMDS (2.3 equivalents) and n-BuLi (2.3 equivalents) at 195 K, (3S)-3-(nosylamino)butano-4-lactone was added. Benzyl bromide (2.1 equivalents) was added to the resultant dianion to afford a mixture of products which, after chromatography, provided (I) in a 42% yield. 1H NMR

(CDCl3 + DMSO, 296 K, p.p.m.): δ 8.30 (s, 1H), 7.95–7.92 (d, 1H), 7.80–7.69 (m, 2H), 7.14–7.02 (m, 5H), 4.19–3.99

(AB of ABX, 2H), 3.94–3.80 (X of ABX, 1H), 3.12 (m, 1H), 3.00–2.97 (m, 2H); 13C NMR (CDCl

3 + DMSO, 296 K,

p.p.m.): δ 175.3, 136.3, 133.7, 133.4, 132.2, 130.3, 129.1, 128.2, 126.5, 124.6, 70.9, 52.8, 45.7, 32.7.

S3. Refinement

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[image:4.610.127.482.67.323.2]

Figure 1

The molecular structure of (I) with displacement ellipsoids shown at the 30% probability level.

(2S,3S)-2-benzyl-3-(nosylamino)butano-4-lactone

Crystal data C17H16N2O6S

Mr = 376.38

Orthorhombic, P212121

a = 7.3711 (5) Å b = 11.0756 (7) Å c = 20.5014 (12) Å V = 1673.72 (18) Å3

Z = 4 F(000) = 784

Dx = 1.494 Mg m−3

Mo radiation, λ = 0.71073 Å Cell parameters from 5380 reflections θ = 2.0–26.0°

µ = 0.23 mm−1

T = 173 K Block, colorless 0.50 × 0.40 × 0.30 mm

Data collection Bruker CCD-1000

diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

Absorption correction: empirical (using intensity measurements)

SADABS(Blessing, 1995) Tmin = 0.893, Tmax = 0.934

7922 measured reflections 3312 independent reflections 3081 reflections with I > 2σ(I) Rint = 0.023

θmax = 26.4°, θmin = 2.0°

h = −9→8 k = −13→13 l = −25→12

Refinement Refinement on F2

Least-squares matrix: full R[F2 > 2σ(F2)] = 0.029

wR(F2) = 0.073

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supporting information

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Acta Cryst. (2002). E58, o65–o66

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

All H-atom parameters refined

w = 1/[σ2(F

o2) + (0.045P)2 + 0.1922P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001

Δρmax = 0.32 e Å−3

Δρmin = −0.27 e Å−3

Absolute structure: Flack (1983) Absolute structure parameter: 0.04 (6)

Special details

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 (Å2)

x y z Uiso*/Ueq

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H11A 0.633 (3) −0.167 (2) 0.9245 (11) 0.040 (6)* H11B 0.425 (3) −0.2158 (18) 0.9185 (9) 0.025 (5)* C12 0.4705 (2) −0.07330 (16) 0.85620 (9) 0.0256 (4) C13 0.3668 (3) −0.1244 (2) 0.80671 (11) 0.0323 (4) H13 0.310 (3) −0.192 (2) 0.8125 (11) 0.037 (6)* C14 0.3429 (3) −0.0660 (2) 0.74782 (11) 0.0395 (5) H14 0.267 (3) −0.1061 (18) 0.7157 (12) 0.037 (6)* C15 0.4208 (3) 0.0453 (2) 0.73718 (10) 0.0373 (5) H15 0.404 (3) 0.0849 (19) 0.6957 (12) 0.038 (6)* C16 0.5214 (3) 0.09874 (18) 0.78649 (10) 0.0325 (5) H16 0.572 (3) 0.178 (2) 0.7795 (11) 0.037 (6)* C17 0.5466 (3) 0.04018 (17) 0.84510 (10) 0.0283 (4) H17 0.611 (3) 0.0745 (17) 0.8795 (10) 0.023 (5)*

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

S 0.0217 (2) 0.0226 (2) 0.0189 (2) 0.00135 (17) 0.00115 (17) 0.00188 (17) O1 0.0550 (9) 0.0213 (7) 0.0409 (9) 0.0015 (6) −0.0095 (7) −0.0027 (6) O2 0.0376 (8) 0.0312 (7) 0.0336 (7) −0.0055 (6) −0.0129 (6) 0.0052 (6) O3 0.0351 (8) 0.0264 (6) 0.0243 (7) 0.0068 (6) 0.0063 (6) 0.0009 (5) O4 0.0256 (6) 0.0341 (7) 0.0291 (7) −0.0033 (6) 0.0009 (6) 0.0073 (6) O5 0.0467 (8) 0.0356 (8) 0.0272 (8) 0.0096 (7) 0.0053 (6) 0.0110 (6) O6 0.0544 (9) 0.0343 (8) 0.0398 (8) 0.0151 (8) −0.0063 (8) 0.0067 (6) N1 0.0279 (8) 0.0244 (8) 0.0197 (7) −0.0014 (6) −0.0006 (6) 0.0025 (6) N2 0.0252 (8) 0.0173 (7) 0.0262 (8) −0.0015 (6) −0.0042 (7) 0.0024 (6) C1 0.0218 (9) 0.0227 (9) 0.0209 (9) 0.0031 (7) −0.0017 (7) −0.0021 (7) C2 0.0249 (9) 0.0238 (9) 0.0234 (9) 0.0045 (8) 0.0024 (7) 0.0034 (8) C3 0.0311 (10) 0.0341 (10) 0.0168 (9) 0.0079 (9) −0.0005 (8) 0.0016 (7) C4 0.0292 (9) 0.0326 (10) 0.0245 (9) 0.0026 (9) −0.0042 (7) −0.0071 (9) C5 0.0241 (8) 0.0259 (9) 0.0271 (9) 0.0006 (7) 0.0000 (7) −0.0017 (8) C6 0.0201 (9) 0.0234 (8) 0.0175 (8) 0.0042 (7) −0.0002 (7) 0.0016 (7) C7 0.0270 (9) 0.0177 (8) 0.0255 (10) −0.0014 (8) −0.0007 (8) 0.0011 (7) C8 0.0450 (13) 0.0335 (11) 0.0331 (12) 0.0109 (10) 0.0097 (10) 0.0112 (9) C9 0.0390 (11) 0.0234 (9) 0.0270 (9) 0.0030 (9) −0.0058 (8) 0.0001 (7) C10 0.0279 (9) 0.0213 (8) 0.0246 (9) 0.0012 (8) −0.0017 (8) 0.0017 (7) C11 0.0379 (10) 0.0243 (9) 0.0289 (10) 0.0054 (8) 0.0040 (8) 0.0003 (7) C12 0.0236 (10) 0.0273 (9) 0.0260 (9) 0.0050 (8) 0.0059 (7) −0.0013 (7) C13 0.0299 (10) 0.0333 (11) 0.0336 (11) −0.0027 (9) 0.0029 (9) −0.0085 (9) C14 0.0336 (11) 0.0544 (15) 0.0305 (12) 0.0072 (11) −0.0044 (9) −0.0122 (10) C15 0.0360 (11) 0.0501 (13) 0.0257 (10) 0.0191 (11) 0.0028 (9) 0.0042 (9) C16 0.0322 (11) 0.0321 (11) 0.0332 (11) 0.0054 (9) 0.0090 (8) 0.0032 (8) C17 0.0257 (10) 0.0322 (10) 0.0269 (10) −0.0014 (8) 0.0023 (8) −0.0037 (8)

Geometric parameters (Å, º)

S—O4 1.4277 (14) C7—C8 1.531 (3)

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Acta Cryst. (2002). E58, o65–o66

S—N2 1.5987 (16) C7—H7 0.867 (19)

S—C6 1.7891 (17) C8—H8A 0.97 (2)

O1—N1 1.2218 (19) C8—H8B 1.00 (2)

O2—N1 1.2203 (19) C9—C10 1.519 (3)

O5—C9 1.342 (2) C10—C11 1.527 (3)

O5—C8 1.443 (2) C10—H10 0.95 (2)

O6—C9 1.197 (2) C11—C12 1.509 (3)

N1—C1 1.473 (2) C11—H11A 1.04 (2)

N2—C7 1.462 (2) C11—H11B 0.99 (2)

N2—H2N 0.78 (2) C12—C13 1.391 (3)

C1—C2 1.378 (2) C12—C17 1.395 (3)

C1—C6 1.394 (2) C13—C14 1.381 (3)

C2—C3 1.390 (3) C13—H13 0.87 (2)

C2—H2 0.93 (2) C14—C15 1.377 (3)

C3—C4 1.382 (3) C14—H14 0.97 (2)

C3—H3 0.94 (2) C15—C16 1.387 (3)

C4—C5 1.389 (3) C15—H15 0.96 (2)

C4—H4 1.00 (2) C16—C17 1.378 (3)

C5—C6 1.383 (3) C16—H16 0.96 (2)

C5—H5 0.96 (2) C17—H17 0.93 (2)

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C4—C5—H5 122.1 (12) C15—C14—H14 122.8 (13) C5—C6—C1 118.21 (17) C13—C14—H14 116.9 (13) C5—C6—S 118.21 (14) C14—C15—C16 119.3 (2) C1—C6—S 123.01 (13) C14—C15—H15 119.6 (13) N2—C7—C8 112.38 (16) C16—C15—H15 121.1 (13) N2—C7—C10 112.79 (15) C17—C16—C15 120.4 (2) C8—C7—C10 103.31 (16) C17—C16—H16 120.4 (13) N2—C7—H7 108.1 (12) C15—C16—H16 119.2 (13) C8—C7—H7 108.9 (13) C16—C17—C12 120.82 (19) C10—C7—H7 111.3 (12) C16—C17—H17 122.5 (12) O5—C8—C7 105.61 (16) C12—C17—H17 116.7 (12)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N2—H2N···O3i 0.78 (2) 2.19 (2) 2.917 (2) 154 (2)

C7—H7···O6ii 0.867 (19) 2.532 (19) 3.269 (2) 143.5 (16)

C2—H2···CgBiii 0.93 (2) 2.66 (2) 3.4214 (18) 139.7 (17)

C14—H14···CgAiv 0.97 (2) 3.17 (2) 3.936 (2) 136.8 (18)

Figure

Figure 1

References

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