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

In the crystalline state, the title mol­ecule, C₁₇H₁₆N₂O₆S, with its five-membered ring in an envelope conformation, produces a three-dimensional network of weak intermolecular hydro­gen-bonding interactions.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.029
• wR factor = 0.073
• Data-to-parameter ratio = 11.1

checkCIF results

No syntax errors found



ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_716  Alert C H...A   Unknown or Inconsistent Label ........       C~G~B
                           H2     C~G~B

PLAT_716  Alert C H...A   Unknown or Inconsistent Label ........       C~G~A
                           H14    C~G~A

PLAT_717  Alert C D...A   Unknown or Inconsistent Label ........       C~G~B
                           C2     C~G~B

PLAT_717  Alert C D...A   Unknown or Inconsistent Label ........       C~G~A
                           C14    C~G~A

PLAT_718  Alert C D-H..A  Unknown or Inconsistent label ........       C~G~B
                           C2     H2     C~G~B

PLAT_718  Alert C D-H..A  Unknown or Inconsistent label ........       C~G~A
                           C14    H14    C~G~A

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           26.40
         From the CIF: _reflns_number_total               3312
         Count of symmetry unique reflns         1986
         Completeness (_total/calc)            166.77%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      1326
         Fraction of Friedel pairs measured     0.668
         Are heavy atom types Z>Si present          yes
          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.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 6 Alert Level C = Please check

---

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; C_gA is the centroid of the C1—C6 ring and C_gB 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 (CDCl₃ + 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

H atoms were located from a difference map and both positional and isotropic displacement parameters were refined. For H atoms, the C—H range is 0.87 (2)–1.03 (2) Å and the N—H distance is 0.78 (2) Å.

Computing details

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

Figures

Fig. 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	Dx = 1.494 Mg m^−3
Mr = 376.38	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 5380 reflections
a = 7.3711 (5) Å	θ = 2.0–26.0°
b = 11.0756 (7) Å	µ = 0.23 mm^−1
c = 20.5014 (12) Å	T = 173 K
V = 1673.72 (18) Å^3	Block, colorless
Z = 4	0.50 × 0.40 × 0.30 mm
F(000) = 784

Data collection

Bruker CCD-1000 diffractometer	3312 independent reflections
Radiation source: fine-focus sealed tube	3081 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ω scans	θmax = 26.4°, θmin = 2.0°
Absorption correction: empirical (using intensity measurements) SADABS(Blessing, 1995)	h = −9→8
Tmin = 0.893, Tmax = 0.934	k = −13→13
7922 measured reflections	l = −25→12

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	All H-atom parameters refined
wR(F^2) = 0.073	w = 1/[σ^2(Fo^2) + (0.045P)^2 + 0.1922P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
3312 reflections	Δρmax = 0.32 e Å^−3
299 parameters	Δρmin = −0.27 e Å^−3
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	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 (Ų)

	x	y	z	Uiso*/Ueq
S	0.06374 (6)	0.16572 (4)	0.93365 (2)	0.02106 (11)
O1	0.2540 (2)	0.49288 (12)	0.87315 (8)	0.0391 (4)
O2	0.39755 (18)	0.33514 (13)	0.90810 (7)	0.0342 (3)
O3	0.03731 (18)	0.28085 (11)	0.96477 (6)	0.0286 (3)
O4	−0.07450 (17)	0.07557 (12)	0.93633 (6)	0.0296 (3)
O5	0.3256 (2)	−0.12213 (13)	1.08185 (7)	0.0365 (4)
O6	0.5701 (2)	−0.22510 (13)	1.05290 (7)	0.0429 (4)
N1	0.2836 (2)	0.38435 (13)	0.87408 (7)	0.0240 (3)
N2	0.2482 (2)	0.10667 (13)	0.95939 (8)	0.0229 (3)
H2N	0.311 (3)	0.156 (2)	0.9746 (11)	0.034 (6)*
C1	0.1805 (2)	0.30776 (15)	0.82852 (8)	0.0218 (4)
C2	0.1804 (2)	0.34321 (17)	0.76410 (9)	0.0241 (4)
H2	0.239 (3)	0.4139 (18)	0.7524 (9)	0.021 (5)*
C3	0.0921 (3)	0.27125 (17)	0.71853 (9)	0.0273 (4)
H3	0.092 (3)	0.2931 (18)	0.6744 (10)	0.033 (6)*
C4	0.0067 (3)	0.16616 (19)	0.73802 (9)	0.0287 (4)
H4	−0.056 (3)	0.1119 (18)	0.7065 (11)	0.037 (6)*
C5	0.0056 (2)	0.13294 (17)	0.80332 (10)	0.0257 (4)
H5	−0.056 (3)	0.062 (2)	0.8184 (10)	0.032 (5)*
C6	0.0935 (2)	0.20293 (15)	0.84940 (8)	0.0204 (4)
C7	0.2602 (3)	−0.01705 (16)	0.98394 (9)	0.0234 (4)
H7	0.184 (3)	−0.0611 (17)	0.9621 (9)	0.016 (5)*
C8	0.2139 (3)	−0.0258 (2)	1.05657 (11)	0.0372 (5)
H8A	0.249 (3)	0.046 (2)	1.0808 (10)	0.031 (6)*
H8B	0.085 (3)	−0.0511 (18)	1.0634 (10)	0.029 (5)*
C9	0.4617 (3)	−0.14788 (16)	1.04065 (9)	0.0298 (4)
C10	0.4527 (3)	−0.06845 (16)	0.98030 (9)	0.0246 (4)
H10	0.537 (3)	−0.0037 (17)	0.9859 (9)	0.024 (5)*
C11	0.4992 (3)	−0.14105 (17)	0.91920 (9)	0.0304 (4)
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)
S—O3	1.4391 (13)	C7—C10	1.531 (3)
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)
O4—S—O3	120.40 (8)	O5—C8—H8A	105.6 (13)
O4—S—N2	107.96 (8)	C7—C8—H8A	112.8 (13)
O3—S—N2	109.35 (9)	O5—C8—H8B	106.6 (12)
O4—S—C6	106.61 (8)	C7—C8—H8B	111.4 (12)
O3—S—C6	103.92 (7)	H8A—C8—H8B	114.0 (18)
N2—S—C6	107.98 (8)	O6—C9—O5	121.25 (18)
C9—O5—C8	110.94 (15)	O6—C9—C10	127.85 (19)
O2—N1—O1	124.85 (16)	O5—C9—C10	110.90 (15)
O2—N1—C1	117.41 (14)	C9—C10—C11	110.68 (15)
O1—N1—C1	117.67 (15)	C9—C10—C7	102.48 (15)
C7—N2—S	123.23 (13)	C11—C10—C7	116.32 (16)
C7—N2—H2N	118.8 (16)	C9—C10—H10	108.0 (12)
S—N2—H2N	110.6 (16)	C11—C10—H10	110.4 (12)
C2—C1—C6	122.12 (16)	C7—C10—H10	108.4 (12)
C2—C1—N1	116.36 (16)	C12—C11—C10	114.14 (15)
C6—C1—N1	121.49 (16)	C12—C11—H11A	111.2 (13)
C1—C2—C3	118.76 (18)	C10—C11—H11A	105.9 (13)
C1—C2—H2	119.3 (12)	C12—C11—H11B	109.0 (11)
C3—C2—H2	122.0 (12)	C10—C11—H11B	109.2 (11)
C4—C3—C2	120.13 (17)	H11A—C11—H11B	107.2 (17)
C4—C3—H3	119.8 (13)	C13—C12—C17	117.94 (18)
C2—C3—H3	120.0 (14)	C13—C12—C11	119.95 (18)
C3—C4—C5	120.29 (18)	C17—C12—C11	122.11 (18)
C3—C4—H4	122.1 (13)	C14—C13—C12	121.2 (2)
C5—C4—H4	117.6 (13)	C14—C13—H13	117.7 (16)
C6—C5—C4	120.48 (18)	C12—C13—H13	121.1 (16)
C6—C5—H5	117.4 (12)	C15—C14—C13	120.3 (2)
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···O3^i	0.78 (2)	2.19 (2)	2.917 (2)	154 (2)
C7—H7···O6^ii	0.867 (19)	2.532 (19)	3.269 (2)	143.5 (16)
C2—H2···CgB^iii	0.93 (2)	2.66 (2)	3.4214 (18)	139.7 (17)
C14—H14···CgA^iv	0.97 (2)	3.17 (2)	3.936 (2)	136.8 (18)

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