Crystal structure of N'-[(E)-(1S,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 C atom adjacent to the quaternary C atom being the flap, and the methyl and isopropyl substituents lying to the same side of the ring. The dihedral angles between the four nearly coplanar atoms of the five-membered ring and the flap and the aromatic ring are 35.74 (15) and 55.72 (9)°, respectively. The bond angles around the S atom are in the range from 103.26 (12) to 120.65 (14)°. In the crystal, mol-ecules are linked via N-H⋯O hydrogen bonds, forming a chain along the a axis.

Related literature

For the synthesis of terpenoid-related buildings blocks, in particular cyclo­penta­noids, see: Helmboldt et al. (2006 ▸); Gille et al. (2011 ▸); Becker et al. (2013 ▸); Tymann et al. (2014 ▸). For the crystal structure of the corresponding trans-diastereomer, see: Tymann et al. (2015 ▸). 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

Orthorhombic,

a = 9.4918 (7) Å

b = 13.2348 (12) Å

c = 14.6691 (12) Å

V = 1842.8 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.19 mm−1

T = 173 K

0.31 × 0.25 × 0.23 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer

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

15093 measured reflections

4215 independent reflections

3526 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.093

S = 1.05

4215 reflections

216 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.33 e Å−3

Absolute structure: Flack x determined using 1277 quotients [(I +)-(I -)]/[(I +)+(I -)] (Parsons & Flack, 2004 ▸)

Absolute structure parameter: −0.02 (4)

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▸); cell refinement: CrysAlis CCD; data reduction: CrysAlis CCD; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ▸); 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, 2887. DOI: 10.1107/S2056989015020307/tk5399sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015020307/tk5399Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015020307/tk5399Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015020307/tk5399fig1.tif

The mol­ecular structure of the title compound, showing the labelling of all non-H atoms. Displacement ellipsoids are shown at the 50% probability level.

CCDC reference: 1037859

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

C17H24N2O3S	Dx = 1.213 Mg m−3
Mr = 336.44	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 3585 reflections
a = 9.4918 (7) Å	θ = 2.6–27.1°
b = 13.2348 (12) Å	µ = 0.19 mm−1
c = 14.6691 (12) Å	T = 173 K
V = 1842.8 (3) Å3	Block, colourless
Z = 4	0.31 × 0.25 × 0.23 mm
F(000) = 720

Oxford Diffraction Xcalibur Sapphire3 diffractometer	4215 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3526 reflections with I > 2σ(I)
Detector resolution: 16.0560 pixels mm-1	Rint = 0.046
φ and ω scans	θmax = 28.0°, θmin = 2.6°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	h = −12→12
Tmin = 0.98, Tmax = 1.00	k = −15→16
15093 measured reflections	l = −19→18

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.093	w = 1/[σ2(Fo2) + (0.0401P)2 + 0.1494P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
4215 reflections	Δρmax = 0.22 e Å−3
216 parameters	Δρmin = −0.33 e Å−3
0 restraints	Absolute structure: Flack x determined using 1277 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (4)

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.

	x	y	z	Uiso*/Ueq
S	0.57466 (7)	0.53116 (6)	0.08855 (5)	0.02777 (17)
O1	0.45052 (19)	0.57619 (18)	0.05053 (14)	0.0389 (6)
O2	0.5837 (2)	0.42449 (16)	0.10068 (15)	0.0411 (5)
O3	1.1776 (2)	0.72234 (15)	−0.00066 (13)	0.0309 (5)
N1	0.6994 (2)	0.5647 (2)	0.01656 (15)	0.0241 (5)
N2	0.8352 (2)	0.53514 (19)	0.04375 (14)	0.0226 (5)
C1	0.7064 (4)	0.7294 (3)	0.4507 (2)	0.0510 (10)
H1A	0.6958	0.6789	0.4990	0.077*
H1B	0.6409	0.7854	0.4614	0.077*
H1C	0.8033	0.7550	0.4506	0.077*
C2	0.6745 (3)	0.6814 (2)	0.35949 (19)	0.0333 (7)
C3	0.7286 (3)	0.5861 (3)	0.3378 (2)	0.0358 (8)
H3	0.7880	0.5526	0.3803	0.043*
C4	0.6978 (3)	0.5398 (2)	0.25650 (18)	0.0308 (6)
H4	0.7341	0.4745	0.2433	0.037*
C5	0.6127 (3)	0.5896 (2)	0.19358 (18)	0.0259 (6)
C6	0.5606 (3)	0.6853 (2)	0.21212 (19)	0.0303 (7)
H6	0.5052	0.7199	0.1681	0.036*
C7	0.5902 (3)	0.7302 (2)	0.2954 (2)	0.0329 (7)
H7	0.5526	0.7950	0.3089	0.039*
C8	0.9350 (3)	0.5757 (2)	−0.00108 (18)	0.0240 (6)
H8	0.9128	0.6228	−0.0478	0.029*
C9	1.0880 (3)	0.5513 (2)	0.01786 (18)	0.0251 (6)
C10	1.1497 (3)	0.6526 (2)	0.05022 (18)	0.0227 (6)
C11	1.1652 (3)	0.6526 (2)	0.15308 (17)	0.0247 (6)
H11	1.2680	0.6440	0.1659	0.030*
C12	1.1208 (3)	0.7517 (2)	0.1995 (2)	0.0320 (7)
H12	1.1814	0.8067	0.1739	0.038*
C13	1.1488 (4)	0.7473 (3)	0.3020 (2)	0.0475 (9)
H13A	1.0847	0.6984	0.3302	0.071*
H13B	1.1332	0.8142	0.3288	0.071*
H13C	1.2464	0.7264	0.3127	0.071*
C14	0.9673 (3)	0.7800 (3)	0.1793 (2)	0.0416 (8)
H14A	0.9047	0.7275	0.2034	0.062*
H14B	0.9538	0.7858	0.1133	0.062*
H14C	0.9451	0.8448	0.2084	0.062*
C15	1.0931 (3)	0.5542 (2)	0.18366 (19)	0.0306 (7)
H15A	1.1406	0.5254	0.2379	0.037*
H15B	0.9927	0.5661	0.1984	0.037*
C16	1.1078 (3)	0.4835 (2)	0.1014 (2)	0.0304 (7)
H16A	1.2019	0.4512	0.1006	0.036*
H16B	1.0349	0.4300	0.1030	0.036*
C17	1.1573 (3)	0.5148 (2)	−0.0706 (2)	0.0359 (7)
H17A	1.2582	0.5039	−0.0602	0.054*
H17B	1.1447	0.5660	−0.1183	0.054*
H17C	1.1135	0.4513	−0.0900	0.054*
H1N	0.690 (3)	0.627 (3)	0.001 (2)	0.040 (10)*

	U11	U22	U33	U12	U13	U23
S	0.0189 (3)	0.0290 (4)	0.0354 (4)	−0.0034 (3)	0.0053 (3)	−0.0060 (3)
O1	0.0171 (10)	0.0542 (15)	0.0455 (12)	0.0008 (10)	−0.0003 (9)	−0.0093 (11)
O2	0.0389 (11)	0.0293 (12)	0.0549 (14)	−0.0106 (10)	0.0121 (11)	−0.0049 (10)
O3	0.0323 (10)	0.0271 (12)	0.0334 (11)	−0.0043 (9)	0.0072 (9)	0.0008 (10)
N1	0.0182 (11)	0.0256 (14)	0.0286 (13)	0.0020 (10)	0.0006 (9)	−0.0015 (10)
N2	0.0177 (10)	0.0213 (12)	0.0286 (11)	0.0023 (10)	0.0013 (9)	−0.0062 (10)
C1	0.077 (3)	0.047 (2)	0.0290 (17)	−0.009 (2)	0.0018 (17)	0.0017 (16)
C2	0.0404 (17)	0.0341 (19)	0.0255 (15)	−0.0055 (15)	0.0097 (13)	0.0052 (12)
C3	0.0395 (17)	0.039 (2)	0.0291 (16)	0.0024 (15)	0.0036 (13)	0.0138 (14)
C4	0.0358 (15)	0.0263 (16)	0.0302 (15)	0.0065 (14)	0.0113 (12)	0.0071 (13)
C5	0.0204 (13)	0.0296 (17)	0.0278 (14)	−0.0006 (11)	0.0080 (11)	0.0012 (12)
C6	0.0249 (15)	0.0327 (17)	0.0334 (16)	0.0049 (14)	0.0025 (12)	−0.0005 (12)
C7	0.0352 (16)	0.0260 (17)	0.0375 (16)	0.0031 (14)	0.0084 (14)	−0.0025 (13)
C8	0.0219 (13)	0.0253 (15)	0.0247 (13)	−0.0015 (12)	0.0019 (11)	−0.0030 (11)
C9	0.0180 (12)	0.0243 (16)	0.0329 (14)	−0.0006 (12)	0.0038 (11)	−0.0059 (11)
C10	0.0126 (12)	0.0245 (16)	0.0310 (14)	0.0022 (11)	0.0036 (11)	−0.0035 (12)
C11	0.0159 (12)	0.0303 (17)	0.0279 (14)	0.0000 (12)	0.0005 (11)	−0.0016 (12)
C12	0.0323 (16)	0.0319 (18)	0.0319 (16)	−0.0016 (13)	0.0042 (12)	−0.0074 (13)
C13	0.054 (2)	0.057 (3)	0.0313 (17)	0.0063 (18)	0.0011 (16)	−0.0120 (16)
C14	0.0392 (18)	0.042 (2)	0.0434 (19)	0.0141 (16)	0.0068 (15)	−0.0046 (15)
C15	0.0272 (14)	0.0316 (17)	0.0330 (15)	0.0023 (13)	−0.0008 (12)	0.0076 (12)
C16	0.0210 (13)	0.0226 (16)	0.0475 (18)	0.0017 (11)	0.0010 (12)	0.0028 (13)
C17	0.0256 (14)	0.041 (2)	0.0417 (17)	−0.0039 (14)	0.0063 (13)	−0.0178 (14)

S—O2	1.426 (2)	C9—C16	1.531 (4)
S—O1	1.433 (2)	C9—C17	1.534 (4)
S—N1	1.648 (2)	C9—C10	1.538 (4)
S—C5	1.761 (3)	C10—C11	1.516 (4)
O3—C10	1.216 (3)	C11—C12	1.537 (4)
N1—N2	1.405 (3)	C11—C15	1.539 (4)
N1—H1N	0.86 (3)	C11—H11	1.0000
N2—C8	1.272 (3)	C12—C13	1.528 (4)
C1—C2	1.511 (4)	C12—C14	1.533 (4)
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—C7	1.393 (4)	C13—H13C	0.9800
C2—C3	1.399 (5)	C14—H14A	0.9800
C3—C4	1.372 (4)	C14—H14B	0.9800
C3—H3	0.9500	C14—H14C	0.9800
C4—C5	1.392 (4)	C15—C16	1.533 (4)
C4—H4	0.9500	C15—H15A	0.9900
C5—C6	1.387 (4)	C15—H15B	0.9900
C6—C7	1.387 (4)	C16—H16A	0.9900
C6—H6	0.9500	C16—H16B	0.9900
C7—H7	0.9500	C17—H17A	0.9800
C8—C9	1.514 (3)	C17—H17B	0.9800
C8—H8	0.9500	C17—H17C	0.9800
O2—S—O1	120.65 (14)	O3—C10—C9	123.7 (2)
O2—S—N1	107.67 (13)	C11—C10—C9	110.1 (2)
O1—S—N1	103.26 (12)	C10—C11—C12	114.4 (2)
O2—S—C5	108.25 (14)	C10—C11—C15	104.3 (2)
O1—S—C5	109.04 (13)	C12—C11—C15	118.2 (2)
N1—S—C5	107.17 (12)	C10—C11—H11	106.4
N2—N1—S	113.73 (18)	C12—C11—H11	106.4
N2—N1—H1N	116 (2)	C15—C11—H11	106.4
S—N1—H1N	111 (2)	C13—C12—C14	111.3 (3)
C8—N2—N1	114.7 (2)	C13—C12—C11	110.8 (3)
C2—C1—H1A	109.5	C14—C12—C11	112.6 (3)
C2—C1—H1B	109.5	C13—C12—H12	107.3
H1A—C1—H1B	109.5	C14—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
C7—C2—C3	118.4 (3)	H13A—C13—H13B	109.5
C7—C2—C1	121.2 (3)	C12—C13—H13C	109.5
C3—C2—C1	120.5 (3)	H13A—C13—H13C	109.5
C4—C3—C2	121.5 (3)	H13B—C13—H13C	109.5
C4—C3—H3	119.3	C12—C14—H14A	109.5
C2—C3—H3	119.3	C12—C14—H14B	109.5
C3—C4—C5	119.2 (3)	H14A—C14—H14B	109.5
C3—C4—H4	120.4	C12—C14—H14C	109.5
C5—C4—H4	120.4	H14A—C14—H14C	109.5
C6—C5—C4	120.6 (3)	H14B—C14—H14C	109.5
C6—C5—S	120.0 (2)	C16—C15—C11	104.3 (2)
C4—C5—S	119.4 (2)	C16—C15—H15A	110.9
C5—C6—C7	119.5 (3)	C11—C15—H15A	110.9
C5—C6—H6	120.3	C16—C15—H15B	110.9
C7—C6—H6	120.3	C11—C15—H15B	110.9
C6—C7—C2	120.8 (3)	H15A—C15—H15B	108.9
C6—C7—H7	119.6	C9—C16—C15	105.1 (2)
C2—C7—H7	119.6	C9—C16—H16A	110.7
N2—C8—C9	122.0 (3)	C15—C16—H16A	110.7
N2—C8—H8	119.0	C9—C16—H16B	110.7
C9—C8—H8	119.0	C15—C16—H16B	110.7
C8—C9—C16	112.9 (2)	H16A—C16—H16B	108.8
C8—C9—C17	108.9 (2)	C9—C17—H17A	109.5
C16—C9—C17	116.1 (2)	C9—C17—H17B	109.5
C8—C9—C10	103.6 (2)	H17A—C17—H17B	109.5
C16—C9—C10	102.6 (2)	C9—C17—H17C	109.5
C17—C9—C10	111.9 (2)	H17A—C17—H17C	109.5
O3—C10—C11	126.2 (3)	H17B—C17—H17C	109.5
O2—S—N1—N2	−55.9 (2)	N2—C8—C9—C17	124.3 (3)
O1—S—N1—N2	175.41 (19)	N2—C8—C9—C10	−116.4 (3)
C5—S—N1—N2	60.3 (2)	C8—C9—C10—O3	−76.0 (3)
S—N1—N2—C8	−167.6 (2)	C16—C9—C10—O3	166.3 (2)
C7—C2—C3—C4	−1.5 (4)	C17—C9—C10—O3	41.2 (4)
C1—C2—C3—C4	178.1 (3)	C8—C9—C10—C11	102.3 (2)
C2—C3—C4—C5	1.1 (4)	C16—C9—C10—C11	−15.4 (3)
C3—C4—C5—C6	0.7 (4)	C17—C9—C10—C11	−140.5 (2)
C3—C4—C5—S	179.2 (2)	O3—C10—C11—C12	40.3 (4)
O2—S—C5—C6	−155.0 (2)	C9—C10—C11—C12	−137.9 (2)
O1—S—C5—C6	−22.0 (3)	O3—C10—C11—C15	171.0 (3)
N1—S—C5—C6	89.2 (2)	C9—C10—C11—C15	−7.3 (3)
O2—S—C5—C4	26.5 (2)	C10—C11—C12—C13	−176.4 (2)
O1—S—C5—C4	159.5 (2)	C15—C11—C12—C13	60.2 (3)
N1—S—C5—C4	−89.3 (2)	C10—C11—C12—C14	58.2 (3)
C4—C5—C6—C7	−2.1 (4)	C15—C11—C12—C14	−65.2 (3)
S—C5—C6—C7	179.4 (2)	C10—C11—C15—C16	27.2 (3)
C5—C6—C7—C2	1.7 (4)	C12—C11—C15—C16	155.5 (2)
C3—C2—C7—C6	0.0 (4)	C8—C9—C16—C15	−78.7 (3)
C1—C2—C7—C6	−179.6 (3)	C17—C9—C16—C15	154.5 (2)
N1—N2—C8—C9	−179.0 (2)	C10—C9—C16—C15	32.2 (2)
N2—C8—C9—C16	−6.2 (4)	C11—C15—C16—C9	−37.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3i	0.86 (3)	2.00 (4)	2.836 (3)	164 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O3i	0.86 (3)	2.00 (4)	2.836 (3)	164 (3)

Symmetry code: (i) .