Crystal structure of (E)-N'-{[(1R,3R)-3-isopropyl-1-methyl-2-oxo-cyclo-pent-yl]methyl-idene}-4-methyl-benzene-sulfono-hydrazide.

The title compound, C17H24N2O3S, was synthesized in order to determine the relative configuration of the corresponding β-keto aldehyde. In the U-shaped mol-ecule, the five-membered ring approximates an envelope with the methyl-ene atom adjacent to the quaternary C atom being the flap. The dihedral angles between the four nearly coplanar atoms of the five-membered ring and the flap and the aromatic ring are 38.8 (4) and 22.9 (2)°, respectively. The bond angles around the S atom are in the range 104.11 (16)-119.95 (16)°. In the crystal, mol-ecules are linked via N-H⋯O by hydrogen bonds, forming a chain along the a-axis direction.

Related literature

For the synthesis of terpenoid-related building blocks, in particular cyclo­penta­noids, see: Becker et al. (2013 ▸); Gille et al. (2011 ▸); Helmboldt et al. (2006 ▸); Nelson et al. (2011 ▸); Tymann et al.(2014 ▸). For a review on cyclo­penta­noids by ring contraction see: Silva (2002 ▸). For a solid–acid catalysed rearrangement of cyclic α,β-ep­oxy ketones see: Elings et al. (2000 ▸).

Experimental

Crystal data

C17H24N2O3S

M = 336.44

Monoclinic,

a = 6.6198 (8) Å

b = 16.8318 (18) Å

c = 7.9506 (9) Å

β = 97.141 (11)°

V = 879.00 (17) Å3

Z = 2

Mo Kα radiation

μ = 0.20 mm−1

T = 173 K

0.23 × 0.10 × 0.03 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis CCD; Oxford Diffraction, 2008 ▸) T min = 0.98, T max = 1.00

6620 measured reflections

3684 independent reflections

3185 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.091

S = 1.01

3684 reflections

216 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.21 e Å−3

Δρmin = −0.29 e Å−3

Absolute structure: Flack x determined using 1307 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons & Flack,2004 ▸)

Absolute structure parameter: 0.02 (5)

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▸); cell refinement: CrysAlis CCD (Oxford Diffraction, 2008 ▸); data reduction: CrysAlis RED (Oxford Diffraction, 2008 ▸); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL-Plus (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008 ▸) and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) I, 2864. DOI: 10.1107/S2056989014026747/tk5349sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014026747/tk5349Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989014026747/tk5349Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989014026747/tk5349fig1.tif

The mol­ecular structure of the title compound, showing the labelling of all non-H atoms. Displacement ellipsoids are shown at the 30% probability level.

CCDC reference: 1037859

Additional supporting information: crystallographic information; 3D view; checkCIF report

C17H24N2O3S	Z = 2
Mr = 336.44	F(000) = 360
Monoclinic, P21	Dx = 1.271 Mg m−3
a = 6.6198 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 16.8318 (18) Å	µ = 0.20 mm−1
c = 7.9506 (9) Å	T = 173 K
β = 97.141 (11)°	Plate, colourless
V = 879.00 (17) Å3	0.23 × 0.10 × 0.03 mm

Oxford Diffraction Xcalibur Sapphire3 diffractometer	3684 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3185 reflections with I > 2σ(I)
Detector resolution: 16.0560 pixels mm-1	Rint = 0.032
phi and ω scans	θmax = 27.0°, θmin = 2.4°
Absorption correction: multi-scan (CrysAlis CCD; Oxford Diffraction, 2008)	h = −7→8
Tmin = 0.98, Tmax = 1.00	k = −21→21
6620 measured reflections	l = −10→9

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.091	w = 1/[σ2(Fo2) + (0.0406P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
3684 reflections	Δρmax = 0.21 e Å−3
216 parameters	Δρmin = −0.29 e Å−3
1 restraint	Absolute structure: Flack x determined using 1307 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack,2004)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (5)

Experimental. Absorption correction: CrysAlis PRO, Agilent Technologies, Version 1.171.36.24 (release 03–12-2012 CrysAlis171. NET) (compiled Dec 3 2012,18:21:49) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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 andgoodness of fit S are based on F2, conventional R-factors R are basedon F, with F set to zero for negative F2. The threshold expression ofF2 > σ(F2) is used only for calculating R-factors(gt) etc. and isnot relevant to the choice of reflections for refinement. R-factors basedon F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
S	0.09218 (13)	0.45682 (4)	0.12604 (10)	0.0211 (2)
O1	0.2056 (4)	0.41202 (15)	0.0179 (3)	0.0301 (7)
O2	−0.1089 (4)	0.43231 (14)	0.1507 (3)	0.0328 (7)
O3	0.7126 (4)	0.64917 (14)	0.0645 (3)	0.0263 (6)
N1	0.0612 (5)	0.54744 (16)	0.0481 (4)	0.0201 (7)
N2	0.2410 (4)	0.59285 (16)	0.0665 (4)	0.0190 (6)
C1	0.6011 (7)	0.4966 (3)	0.8060 (5)	0.0363 (10)
H1A	0.6121	0.5531	0.8347	0.054*
H1B	0.7374	0.4746	0.8012	0.054*
H1C	0.5358	0.4684	0.8926	0.054*
C2	0.4754 (6)	0.4867 (2)	0.6364 (5)	0.0233 (8)
C4	0.4451 (5)	0.4458 (2)	0.3415 (4)	0.0209 (8)
H4	0.5048	0.4249	0.2483	0.025*
C3	0.5595 (5)	0.4551 (2)	0.4991 (4)	0.0233 (7)
H3	0.6986	0.4396	0.5133	0.028*
C5	0.2427 (5)	0.46758 (19)	0.3241 (4)	0.0185 (7)
C6	0.1547 (6)	0.4995 (2)	0.4585 (5)	0.0251 (8)
H6	0.0157	0.5151	0.4435	0.030*
C7	0.2701 (6)	0.5084 (2)	0.6137 (5)	0.0277 (9)
H7	0.2095	0.5295	0.7063	0.033*
C8	0.2181 (5)	0.66745 (19)	0.0519 (4)	0.0190 (7)
H8	0.0848	0.6889	0.0286	0.023*
C9	0.3979 (6)	0.7225 (2)	0.0708 (5)	0.0206 (8)
C10	0.5880 (5)	0.67705 (19)	0.1474 (5)	0.0199 (8)
C11	0.6049 (6)	0.6771 (2)	0.3399 (5)	0.0229 (8)
H11	0.5766	0.6223	0.3794	0.027*
C12	0.8215 (6)	0.7019 (2)	0.4184 (5)	0.0260 (9)
H12	0.9204	0.6689	0.3633	0.031*
C13	0.8553 (7)	0.6835 (3)	0.6095 (5)	0.0462 (12)
H13A	0.9966	0.6954	0.6544	0.069*
H13B	0.8275	0.6271	0.6276	0.069*
H13C	0.7633	0.7161	0.6681	0.069*
C14	0.8694 (6)	0.7886 (2)	0.3864 (5)	0.0331 (10)
H14A	0.7745	0.8227	0.4385	0.050*
H14B	0.8555	0.7986	0.2641	0.050*
H14C	1.0091	0.8005	0.4361	0.050*
C15	0.4298 (6)	0.7325 (2)	0.3774 (5)	0.0283 (9)
H15A	0.3113	0.7012	0.4040	0.034*
H15B	0.4747	0.7677	0.4747	0.034*
C16	0.3749 (6)	0.7811 (2)	0.2166 (5)	0.0282 (9)
H16A	0.4683	0.8268	0.2132	0.034*
H16B	0.2334	0.8011	0.2095	0.034*
C17	0.4217 (6)	0.7612 (2)	−0.0986 (5)	0.0296 (10)
H17A	0.4403	0.7200	−0.1823	0.044*
H17B	0.5406	0.7964	−0.0853	0.044*
H17C	0.2994	0.7923	−0.1372	0.044*
H1N	−0.051 (6)	0.572 (2)	0.079 (5)	0.027 (11)*

	U11	U22	U33	U12	U13	U23
S	0.0204 (5)	0.0192 (4)	0.0219 (4)	−0.0035 (4)	−0.0047 (3)	0.0012 (4)
O1	0.0387 (18)	0.0257 (13)	0.0233 (14)	0.0052 (12)	−0.0065 (13)	−0.0048 (11)
O2	0.0232 (16)	0.0337 (15)	0.0382 (16)	−0.0125 (11)	−0.0090 (12)	0.0108 (12)
O3	0.0152 (14)	0.0305 (14)	0.0335 (15)	0.0027 (11)	0.0039 (12)	−0.0092 (12)
N1	0.0120 (16)	0.0218 (16)	0.0252 (17)	−0.0016 (12)	−0.0024 (13)	0.0021 (13)
N2	0.0129 (16)	0.0229 (15)	0.0209 (16)	−0.0022 (12)	0.0005 (12)	0.0003 (12)
C1	0.046 (3)	0.032 (2)	0.027 (2)	−0.004 (2)	−0.009 (2)	−0.0023 (18)
C2	0.029 (2)	0.0184 (18)	0.021 (2)	−0.0061 (15)	−0.0019 (17)	0.0027 (14)
C4	0.0215 (19)	0.0194 (19)	0.0217 (17)	0.0011 (16)	0.0023 (14)	0.0007 (15)
C3	0.0167 (17)	0.0217 (16)	0.0296 (18)	0.0004 (17)	−0.0053 (14)	0.0021 (19)
C5	0.0200 (18)	0.0157 (18)	0.0188 (16)	−0.0015 (14)	−0.0018 (14)	0.0005 (14)
C6	0.020 (2)	0.0289 (19)	0.026 (2)	0.0013 (16)	0.0034 (17)	0.0025 (16)
C7	0.034 (2)	0.028 (2)	0.021 (2)	0.0013 (17)	0.0071 (18)	−0.0025 (16)
C8	0.0119 (18)	0.0218 (18)	0.0229 (18)	0.0016 (14)	0.0008 (14)	−0.0003 (15)
C9	0.0154 (19)	0.0183 (18)	0.029 (2)	−0.0004 (14)	0.0039 (16)	0.0001 (15)
C10	0.014 (2)	0.0154 (17)	0.031 (2)	−0.0055 (14)	0.0051 (16)	−0.0030 (15)
C11	0.019 (2)	0.0229 (19)	0.027 (2)	−0.0016 (15)	0.0032 (16)	0.0008 (16)
C12	0.017 (2)	0.035 (2)	0.026 (2)	0.0014 (15)	0.0024 (17)	−0.0061 (17)
C13	0.037 (3)	0.067 (3)	0.034 (3)	−0.001 (2)	0.000 (2)	−0.002 (2)
C14	0.021 (2)	0.038 (2)	0.041 (2)	−0.0060 (17)	0.0044 (19)	−0.0082 (19)
C15	0.021 (2)	0.035 (2)	0.030 (2)	−0.0016 (17)	0.0063 (17)	−0.0097 (18)
C16	0.020 (2)	0.0221 (18)	0.043 (2)	0.0017 (15)	0.0068 (18)	−0.0071 (17)
C17	0.024 (2)	0.028 (2)	0.037 (2)	0.0000 (16)	0.0047 (19)	0.0094 (17)

S—O1	1.426 (3)	C9—C17	1.522 (5)
S—O2	1.431 (3)	C9—C10	1.533 (5)
S—N1	1.649 (3)	C9—C16	1.544 (5)
S—C5	1.765 (3)	C10—C11	1.520 (5)
O3—C10	1.213 (4)	C11—C15	1.546 (5)
N1—N2	1.407 (4)	C11—C12	1.548 (5)
N1—H1N	0.91 (4)	C11—H11	1.0000
N2—C8	1.268 (4)	C12—C14	1.522 (6)
C1—C2	1.503 (5)	C12—C13	1.539 (5)
C1—H1A	0.9800	C12—H12	1.0000
C1—H1B	0.9800	C13—H13A	0.9800
C1—H1C	0.9800	C13—H13B	0.9800
C2—C3	1.391 (5)	C13—H13C	0.9800
C2—C7	1.398 (5)	C14—H14A	0.9800
C4—C5	1.380 (5)	C14—H14B	0.9800
C4—C3	1.390 (5)	C14—H14C	0.9800
C4—H4	0.9500	C15—C16	1.523 (6)
C3—H3	0.9500	C15—H15A	0.9900
C5—C6	1.387 (5)	C15—H15B	0.9900
C6—C7	1.376 (5)	C16—H16A	0.9900
C6—H6	0.9500	C16—H16B	0.9900
C7—H7	0.9500	C17—H17A	0.9800
C8—C9	1.501 (5)	C17—H17B	0.9800
C8—H8	0.9500	C17—H17C	0.9800
O1—S—O2	119.95 (16)	O3—C10—C9	123.9 (3)
O1—S—N1	108.22 (16)	C11—C10—C9	110.7 (3)
O2—S—N1	104.11 (16)	C10—C11—C15	103.4 (3)
O1—S—C5	108.13 (16)	C10—C11—C12	110.8 (3)
O2—S—C5	109.82 (16)	C15—C11—C12	116.0 (3)
N1—S—C5	105.67 (15)	C10—C11—H11	108.8
N2—N1—S	113.5 (2)	C15—C11—H11	108.8
N2—N1—H1N	116 (2)	C12—C11—H11	108.8
S—N1—H1N	113 (2)	C14—C12—C13	110.5 (3)
C8—N2—N1	116.0 (3)	C14—C12—C11	113.1 (3)
C2—C1—H1A	109.5	C13—C12—C11	110.9 (3)
C2—C1—H1B	109.5	C14—C12—H12	107.3
H1A—C1—H1B	109.5	C13—C12—H12	107.3
C2—C1—H1C	109.5	C11—C12—H12	107.3
H1A—C1—H1C	109.5	C12—C13—H13A	109.5
H1B—C1—H1C	109.5	C12—C13—H13B	109.5
C3—C2—C7	118.4 (3)	H13A—C13—H13B	109.5
C3—C2—C1	121.0 (4)	C12—C13—H13C	109.5
C7—C2—C1	120.6 (4)	H13A—C13—H13C	109.5
C5—C4—C3	118.3 (3)	H13B—C13—H13C	109.5
C5—C4—H4	120.8	C12—C14—H14A	109.5
C3—C4—H4	120.8	C12—C14—H14B	109.5
C4—C3—C2	121.6 (3)	H14A—C14—H14B	109.5
C4—C3—H3	119.2	C12—C14—H14C	109.5
C2—C3—H3	119.2	H14A—C14—H14C	109.5
C4—C5—C6	121.4 (3)	H14B—C14—H14C	109.5
C4—C5—S	119.7 (3)	C16—C15—C11	105.5 (3)
C6—C5—S	118.8 (3)	C16—C15—H15A	110.6
C7—C6—C5	119.5 (3)	C11—C15—H15A	110.6
C7—C6—H6	120.2	C16—C15—H15B	110.6
C5—C6—H6	120.2	C11—C15—H15B	110.6
C6—C7—C2	120.7 (3)	H15A—C15—H15B	108.8
C6—C7—H7	119.7	C15—C16—C9	104.6 (3)
C2—C7—H7	119.7	C15—C16—H16A	110.8
N2—C8—C9	121.2 (3)	C9—C16—H16A	110.8
N2—C8—H8	119.4	C15—C16—H16B	110.8
C9—C8—H8	119.4	C9—C16—H16B	110.8
C8—C9—C17	110.1 (3)	H16A—C16—H16B	108.9
C8—C9—C10	109.5 (3)	C9—C17—H17A	109.5
C17—C9—C10	113.3 (3)	C9—C17—H17B	109.5
C8—C9—C16	108.5 (3)	H17A—C17—H17B	109.5
C17—C9—C16	114.9 (3)	C9—C17—H17C	109.5
C10—C9—C16	100.0 (3)	H17A—C17—H17C	109.5
O3—C10—C11	125.3 (3)	H17B—C17—H17C	109.5
O1—S—N1—N2	−71.4 (3)	N2—C8—C9—C10	−13.1 (5)
O2—S—N1—N2	159.9 (2)	N2—C8—C9—C16	−121.3 (3)
C5—S—N1—N2	44.2 (3)	C8—C9—C10—O3	97.8 (4)
S—N1—N2—C8	−161.8 (3)	C17—C9—C10—O3	−25.6 (5)
C5—C4—C3—C2	−0.9 (5)	C16—C9—C10—O3	−148.4 (3)
C7—C2—C3—C4	0.7 (5)	C8—C9—C10—C11	−86.2 (4)
C1—C2—C3—C4	−179.9 (3)	C17—C9—C10—C11	150.5 (3)
C3—C4—C5—C6	1.2 (5)	C16—C9—C10—C11	27.7 (4)
C3—C4—C5—S	179.9 (3)	O3—C10—C11—C15	169.9 (3)
O1—S—C5—C4	10.2 (3)	C9—C10—C11—C15	−6.1 (4)
O2—S—C5—C4	142.7 (3)	O3—C10—C11—C12	45.0 (5)
N1—S—C5—C4	−105.5 (3)	C9—C10—C11—C12	−131.0 (3)
O1—S—C5—C6	−171.1 (3)	C10—C11—C12—C14	68.4 (4)
O2—S—C5—C6	−38.5 (3)	C15—C11—C12—C14	−49.0 (4)
N1—S—C5—C6	73.2 (3)	C10—C11—C12—C13	−166.7 (3)
C4—C5—C6—C7	−1.2 (5)	C15—C11—C12—C13	75.8 (4)
S—C5—C6—C7	−179.9 (3)	C10—C11—C15—C16	−18.9 (4)
C5—C6—C7—C2	0.9 (6)	C12—C11—C15—C16	102.6 (4)
C3—C2—C7—C6	−0.7 (5)	C11—C15—C16—C9	37.0 (4)
C1—C2—C7—C6	179.9 (3)	C8—C9—C16—C15	75.9 (4)
N1—N2—C8—C9	179.3 (3)	C17—C9—C16—C15	−160.4 (3)
N2—C8—C9—C17	112.1 (4)	C10—C9—C16—C15	−38.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3i	0.91 (4)	2.03 (4)	2.889 (4)	158 (3)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1NO3i	0.91(4)	2.03(4)	2.889(4)	158(3)

Symmetry code: (i) .