Deacetyl tenuazonic acid p-toluene-sulfonyl-hydrazone.

The title compound {systematic name: 4-methyl-N'-[(3E)-2-(1-methyl-prop-yl)-5-oxopyrrolidin-3-yl-idene]benzene-sulfono-hydrazide}, C(15)H(21)N(3)O(3)S, is the condensation product of deacetyl tenuazonic acid (DTA) and p-toluene-sulfonohydrazide. The crystal structure consists of chains along [100] linked by N-H⋯O hydrogen bonds.

Related literature

For the occurrence of tenuazonic acid (TA) in various food matrices, see: Weidenbörner (2001 ▶). For potential uses of the title compound in food analysis, see: Siegel, Rasenko et al. (2009 ▶). For the crystal structure of DTA, see: Siegel, Koch et al. (2009 ▶) and for its synthesis, see: Lebrun et al. (1988 ▶); Stickings (1959 ▶). For the structure of p-toluene­sulfonyl­hydrazine, see: Roy & Nangia (2007 ▶). For the structures of other p-toluene­sulfonyhydrazones, see, for example: Glidewell et al. (2004 ▶); Ng (1997 ▶); Yan et al. (2008 ▶).

Experimental

Crystal data

C15H21N3O3S

M = 323.41

Orthorhombic,

a = 5.1286 (16) Å

b = 8.285 (3) Å

c = 38.430 (12) Å

V = 1633.0 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.21 mm−1

T = 294 K

0.14 × 0.12 × 0.02 mm

Data collection

Bruker APEX CCD area-detector diffractometer

Absorption correction: ψ scan (SHELXTL; Bruker, 2001 ▶) T min = 0.970, T max = 0.995

13112 measured reflections

4755 independent reflections

2233 reflections with I > 2σ(I)

R int = 0.102

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.097

S = 0.77

4755 reflections

196 parameters

H-atom parameters constrained

Δρmax = 0.21 e Å−3

Δρmin = −0.29 e Å−3

Absolute structure: Flack (1983 ▶), 1905 Friedel pairs

Flack parameter: −0.11 (10)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and ORTEPIII (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809048958/sj2674sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809048958/sj2674Isup2.hkl

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

C15H21N3O3S	F(000) = 688
Mr = 323.41	Dx = 1.315 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 122 reflections
a = 5.1286 (16) Å	θ = 4–23°
b = 8.285 (3) Å	µ = 0.21 mm−1
c = 38.430 (12) Å	T = 294 K
V = 1633.0 (9) Å3	Needle, colourless
Z = 4	0.14 × 0.12 × 0.02 mm

Bruker APEX CCD area-detector diffractometer	4755 independent reflections
Radiation source: fine-focus sealed tube	2233 reflections with I > 2σ(I)
graphite	Rint = 0.102
ω/2θ scans	θmax = 31.1°, θmin = 2.1°
Absorption correction: ψ scan (SHELXTL; Bruker, 2001)	h = −7→7
Tmin = 0.970, Tmax = 0.995	k = −12→12
13112 measured reflections	l = −55→55

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045	H-atom parameters constrained
wR(F2) = 0.097	w = 1/[σ2(Fo2) + (0.0333P)2] where P = (Fo2 + 2Fc2)/3
S = 0.77	(Δ/σ)max = 0.008
4755 reflections	Δρmax = 0.21 e Å−3
196 parameters	Δρmin = −0.28 e Å−3
0 restraints	Absolute structure: Flack (1983), 1905 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.11 (10)

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
S1	0.74721 (13)	0.49291 (7)	0.097917 (14)	0.04011 (15)
O1	−0.0629 (4)	0.3828 (2)	0.23977 (4)	0.0606 (5)
O2	0.6752 (4)	0.63657 (18)	0.08020 (4)	0.0527 (5)
O3	1.0099 (3)	0.4666 (2)	0.10814 (4)	0.0519 (5)
N1	0.5727 (4)	0.4954 (2)	0.13411 (4)	0.0390 (4)
H1	0.3769	0.5132	0.1302	0.047*
N2	0.6024 (4)	0.3487 (2)	0.15275 (5)	0.0383 (5)
N3	0.2395 (4)	0.1958 (2)	0.22262 (5)	0.0448 (5)
H3	0.1936	0.1221	0.2371	0.054*
C1	0.4445 (5)	0.3286 (3)	0.17784 (6)	0.0347 (5)
C2	0.2331 (6)	0.4344 (3)	0.19185 (6)	0.0462 (6)
H2A	0.3038	0.5354	0.2005	0.055*
H2B	0.1039	0.4574	0.1741	0.055*
C3	0.1172 (5)	0.3376 (3)	0.22082 (6)	0.0445 (6)
C4	0.4556 (5)	0.1730 (3)	0.19850 (6)	0.0364 (6)
H4	0.6190	0.1700	0.2117	0.044*
C5	0.4380 (4)	0.0220 (3)	0.17583 (5)	0.0366 (5)
H5	0.5686	0.0339	0.1574	0.044*
C6	0.1756 (4)	0.0098 (3)	0.15812 (6)	0.0542 (7)
H6A	0.1396	0.1114	0.1465	0.065*
H6B	0.0428	−0.0054	0.1758	0.065*
C7	0.1531 (6)	−0.1253 (4)	0.13175 (7)	0.0741 (10)
H7A	0.2885	−0.1145	0.1147	0.111*
H7B	−0.0139	−0.1197	0.1205	0.111*
H7C	0.1703	−0.2274	0.1433	0.111*
C8	0.5103 (4)	−0.1307 (2)	0.19639 (5)	0.0529 (8)
H8A	0.6778	−0.1162	0.2071	0.079*
H8B	0.5166	−0.2214	0.1809	0.079*
H8C	0.3816	−0.1498	0.2141	0.079*
C9	0.6413 (3)	0.32472 (18)	0.07366 (4)	0.0374 (6)
C10	0.7575 (3)	0.17800 (18)	0.07827 (4)	0.0494 (6)
H10	0.8985	0.1674	0.0933	0.059*
C11	0.6641 (6)	0.0458 (3)	0.06047 (7)	0.0565 (8)
H11	0.7440	−0.0539	0.0637	0.068*
C12	0.4556 (6)	0.0576 (3)	0.03813 (7)	0.0529 (7)
C13	0.3442 (6)	0.2071 (4)	0.03385 (7)	0.0593 (8)
H13	0.2038	0.2183	0.0187	0.071*
C14	0.4359 (5)	0.3420 (3)	0.05156 (6)	0.0488 (7)
H14	0.3583	0.4424	0.0483	0.059*
C15	0.3523 (7)	−0.0880 (4)	0.01904 (8)	0.0868 (11)
H15A	0.4174	−0.0880	−0.0044	0.130*
H15B	0.1652	−0.0843	0.0186	0.130*
H15C	0.4083	−0.1844	0.0307	0.130*

	U11	U22	U33	U12	U13	U23
S1	0.0445 (3)	0.0340 (3)	0.0418 (3)	−0.0070 (4)	0.0058 (3)	0.0019 (3)
O1	0.0621 (12)	0.0658 (13)	0.0540 (11)	−0.0020 (10)	0.0229 (11)	−0.0140 (9)
O2	0.0702 (14)	0.0343 (10)	0.0538 (10)	−0.0042 (9)	0.0046 (10)	0.0118 (8)
O3	0.0363 (9)	0.0603 (12)	0.0590 (10)	−0.0088 (9)	0.0040 (8)	−0.0056 (9)
N1	0.0412 (10)	0.0320 (10)	0.0438 (10)	−0.0030 (11)	0.0070 (9)	0.0008 (10)
N2	0.0399 (11)	0.0344 (11)	0.0405 (11)	−0.0056 (9)	0.0043 (11)	0.0034 (9)
N3	0.0547 (13)	0.0410 (12)	0.0387 (11)	−0.0104 (13)	0.0126 (12)	0.0005 (9)
C1	0.0347 (13)	0.0331 (13)	0.0364 (13)	−0.0067 (11)	−0.0005 (12)	−0.0063 (11)
C2	0.0526 (16)	0.0364 (13)	0.0497 (14)	−0.0069 (14)	0.0110 (14)	−0.0034 (10)
C3	0.0502 (16)	0.0458 (17)	0.0375 (14)	−0.0101 (14)	0.0051 (13)	−0.0131 (12)
C4	0.0351 (14)	0.0401 (14)	0.0339 (13)	−0.0102 (12)	0.0025 (11)	0.0021 (11)
C5	0.0367 (13)	0.0353 (14)	0.0378 (12)	0.0002 (12)	0.0025 (10)	0.0004 (11)
C6	0.0496 (16)	0.0443 (15)	0.0685 (17)	0.0041 (14)	−0.0143 (13)	−0.0161 (15)
C7	0.088 (3)	0.0531 (19)	0.082 (2)	0.0056 (17)	−0.0259 (19)	−0.0128 (16)
C8	0.061 (2)	0.0438 (17)	0.0543 (17)	−0.0015 (14)	0.0013 (14)	0.0120 (13)
C9	0.0390 (15)	0.0374 (14)	0.0357 (14)	−0.0051 (12)	0.0044 (12)	0.0051 (11)
C10	0.0548 (16)	0.0423 (14)	0.0511 (15)	0.0011 (17)	−0.0117 (15)	0.0008 (12)
C11	0.071 (2)	0.0400 (17)	0.0582 (17)	0.0025 (13)	−0.0077 (15)	0.0011 (12)
C12	0.0618 (19)	0.0510 (18)	0.0460 (16)	−0.0095 (15)	−0.0003 (15)	−0.0076 (13)
C13	0.0557 (19)	0.071 (2)	0.0515 (17)	0.0002 (16)	−0.0091 (15)	−0.0086 (15)
C14	0.0549 (17)	0.0453 (16)	0.0462 (15)	0.0059 (14)	−0.0019 (14)	−0.0006 (12)
C15	0.104 (3)	0.068 (2)	0.089 (2)	−0.014 (2)	−0.015 (2)	−0.0270 (18)

S1—O3	1.4200 (17)	C6—H6A	0.9700
S1—O2	1.4201 (16)	C6—H6B	0.9700
S1—N1	1.6542 (18)	C7—H7A	0.9600
S1—C9	1.7624 (18)	C7—H7B	0.9600
O1—C3	1.235 (3)	C7—H7C	0.9600
N1—N2	1.419 (2)	C8—H8A	0.9600
N1—H1	1.0263	C8—H8B	0.9600
N2—C1	1.270 (3)	C8—H8C	0.9600
N3—C3	1.333 (3)	C9—C10	1.3653
N3—C4	1.457 (3)	C9—C14	1.361 (3)
N3—H3	0.8600	C10—C11	1.377 (3)
C1—C2	1.494 (3)	C10—H10	0.9300
C1—C4	1.515 (3)	C11—C12	1.375 (4)
C2—C3	1.495 (3)	C11—H11	0.9300
C2—H2A	0.9700	C12—C13	1.374 (4)
C2—H2B	0.9700	C12—C15	1.508 (4)
C4—C5	1.527 (3)	C13—C14	1.391 (3)
C4—H4	0.9800	C13—H13	0.9300
C5—C6	1.511 (3)	C14—H14	0.9300
C5—C8	1.537 (3)	C15—H15A	0.9600
C5—H5	0.9800	C15—H15B	0.9600
C6—C7	1.515 (3)	C15—H15C	0.9600
O3—S1—O2	120.52 (11)	C5—C6—H6B	108.6
O3—S1—N1	106.41 (10)	C7—C6—H6B	108.6
O2—S1—N1	104.60 (10)	H6A—C6—H6B	107.6
O3—S1—C9	108.51 (10)	C6—C7—H7A	109.5
O2—S1—C9	109.21 (9)	C6—C7—H7B	109.5
N1—S1—C9	106.72 (9)	H7A—C7—H7B	109.5
N2—N1—S1	110.85 (14)	C6—C7—H7C	109.5
N2—N1—H1	107.6	H7A—C7—H7C	109.5
S1—N1—H1	114.1	H7B—C7—H7C	109.5
C1—N2—N1	115.28 (18)	C5—C8—H8A	109.5
C3—N3—C4	116.02 (19)	C5—C8—H8B	109.5
C3—N3—H3	122.0	H8A—C8—H8B	109.5
C4—N3—H3	122.0	C5—C8—H8C	109.5
N2—C1—C2	131.2 (2)	H8A—C8—H8C	109.5
N2—C1—C4	119.1 (2)	H8B—C8—H8C	109.5
C2—C1—C4	109.71 (19)	C10—C9—C14	120.84 (13)
C3—C2—C1	104.0 (2)	C10—C9—S1	120.06 (6)
C3—C2—H2A	111.0	C14—C9—S1	119.04 (15)
C1—C2—H2A	111.0	C9—C10—C11	119.48 (14)
C3—C2—H2B	111.0	C9—C10—H10	120.3
C1—C2—H2B	111.0	C11—C10—H10	120.3
H2A—C2—H2B	109.0	C12—C11—C10	121.6 (2)
O1—C3—N3	126.1 (2)	C12—C11—H11	119.2
O1—C3—C2	125.0 (2)	C10—C11—H11	119.2
N3—C3—C2	108.9 (2)	C11—C12—C13	117.5 (2)
N3—C4—C1	101.24 (19)	C11—C12—C15	121.4 (3)
N3—C4—C5	115.09 (18)	C13—C12—C15	121.1 (3)
C1—C4—C5	113.32 (18)	C12—C13—C14	121.7 (3)
N3—C4—H4	109.0	C12—C13—H13	119.2
C1—C4—H4	109.0	C14—C13—H13	119.2
C5—C4—H4	109.0	C9—C14—C13	118.8 (2)
C6—C5—C4	111.3 (2)	C9—C14—H14	120.6
C6—C5—C8	113.0 (2)	C13—C14—H14	120.6
C4—C5—C8	111.52 (17)	C12—C15—H15A	109.5
C6—C5—H5	106.8	C12—C15—H15B	109.5
C4—C5—H5	106.8	H15A—C15—H15B	109.5
C8—C5—H5	106.8	C12—C15—H15C	109.5
C5—C6—C7	114.8 (2)	H15A—C15—H15C	109.5
C5—C6—H6A	108.6	H15B—C15—H15C	109.5
C7—C6—H6A	108.6
O3—S1—N1—N2	−58.11 (17)	N3—C4—C5—C8	−76.8 (2)
O2—S1—N1—N2	173.28 (14)	C1—C4—C5—C8	167.36 (18)
C9—S1—N1—N2	57.61 (15)	C4—C5—C6—C7	172.9 (2)
S1—N1—N2—C1	−169.08 (16)	C8—C5—C6—C7	−60.6 (3)
N1—N2—C1—C2	−1.3 (4)	O3—S1—C9—C10	24.73 (9)
N1—N2—C1—C4	177.98 (18)	O2—S1—C9—C10	157.88 (8)
N2—C1—C2—C3	178.5 (2)	N1—S1—C9—C10	−89.58 (8)
C4—C1—C2—C3	−0.8 (2)	O3—S1—C9—C14	−158.08 (16)
C4—N3—C3—O1	−177.0 (2)	O2—S1—C9—C14	−24.93 (18)
C4—N3—C3—C2	3.1 (3)	N1—S1—C9—C14	87.61 (17)
C1—C2—C3—O1	178.9 (2)	C14—C9—C10—C11	−0.46 (17)
C1—C2—C3—N3	−1.3 (3)	S1—C9—C10—C11	176.68 (18)
C3—N3—C4—C1	−3.4 (2)	C9—C10—C11—C12	−0.1 (3)
C3—N3—C4—C5	−126.0 (2)	C10—C11—C12—C13	0.6 (4)
N2—C1—C4—N3	−177.1 (2)	C10—C11—C12—C15	−179.3 (2)
C2—C1—C4—N3	2.3 (2)	C11—C12—C13—C14	−0.5 (4)
N2—C1—C4—C5	−53.3 (3)	C15—C12—C13—C14	179.4 (3)
C2—C1—C4—C5	126.1 (2)	C10—C9—C14—C13	0.5 (3)
N3—C4—C5—C6	50.5 (3)	S1—C9—C14—C13	−176.63 (18)
C1—C4—C5—C6	−65.4 (3)	C12—C13—C14—C9	0.0 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1i	0.86	2.27	3.104 (3)	162
N1—H1···O3ii	1.03	2.10	3.063 (3)	156

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O1i	0.86	2.27	3.104 (3)	162
N1—H1⋯O3ii	1.03	2.10	3.063 (3)	156

Symmetry codes: (i) ; (ii) .