3-{1-[(2,4-Dinitrophenyl)hydrazino]­ethyl­idene}-5-(1-methylpropyl)pyrrolidine-2,4-dione

Siegel, D.; Merkel, S.; Koch, M.; Emmerling, F.; Nehls, I.

doi:10.1107/S1600536809012458

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Pages o988-o989

doi:10.1107/S1600536809012458

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3-{1-[(2,4-Dinitrophenyl)hydrazino]ethylidene}-5-(1-methylpropyl)pyrrolidine-2,4-dione

David Siegel,^a ^* Stefan Merkel,^a Matthias Koch,^a Franziska Emmerling ^a and Irene Nehls ^a

^aBundesanstalt für Materialforschung und -prüfung, Abteilung Analytische Chemie; Referenzmaterialien, Richard-Willstätter-Strasse 11, D-12489 Berlin-Adlershof, Germany
^*Correspondence e-mail: david.siegel@bam.de

(Received 26 February 2009; accepted 2 April 2009; online 8 April 2009)

In the title compound, C₁₆H₁₉N₅O₆, two intramolecular N—H⋯O hydrogen bonds help to establish the conformation. In the crystal, intermolecular N—H⋯O links result in chains propagating in [010].

Related literature

For the use of the title compound in instrumental analytical chemistry, see: Siegel et al. (2009 ). For the crystal structure of the tenuazonic copper(II) salt, see: Dippenaar et al. (1977 ). For the structures of other 2,4-dinitrophenylhydrazones, see: Tameem et al. (2006 ); Monfared et al. (2007 ); Valente et al. (2008 ); Yin et al. (2008 ). Solubilized tetramic acids and their hydrazones display a variety of tautomeric forms, see: Gelin et al. (1982 ); Nolte et al. (1980 ); Royles (1995 ); Yamaguchi et al. (1976a , 1976b ). For the synthesis, see: Lebrun et al. (1988 ).

Experimental

Crystal data

C₁₆H₁₉N₅O₆
M_r = 377.36
Monoclinic, P 2₁
a = 10.6710 (10) Å
b = 4.9387 (5) Å
c = 16.839 (2) Å
β = 107.363 (4)°
V = 846.98 (15) Å³
Z = 2
Cu Kα radiation
μ = 0.98 mm⁻¹
T = 193 K
0.64 × 0.06 × 0.06 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971 ) T_min = 0.78, T_max = 0.94
3890 measured reflections
3282 independent reflections
3103 reflections with I > 2σ(I)
R_int = 0.025
3 standard reflections frequency: 60 min intensity decay: 2%

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.111
S = 0.99
3282 reflections
247 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Absolute structure: (Flack,1983 )
Flack parameter: 0.1 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯O2	0.93	1.99	2.630 (2)	125
N4—H4N⋯O5	0.89	2.00	2.710 (2)	135
N3—H3N⋯O5ⁱ	0.93	2.36	2.949 (2)	121
N4—H4N⋯O5ⁱ	0.89	2.43	2.898 (2)	113
N5—H5N⋯O2ⁱⁱ	0.86	2.48	3.293 (2)	159
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+1, y-{\script{3\over 2}}, -z+1]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: CORINC (Dräger & Gattow, 1971); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809012458/kj2118sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809012458/kj2118Isup2.hkl

checkCIF report

Comment top

The title compound is the condensation product of the Alternaria spp. mycotoxin tenuazonic acid and 2,4-dinitrophenylhydrazine. It is formed during the derivatization step of a novel HPLC-ESI multistage MS method for tenuazonic acid quantification in cereals (Siegel et al., 2009). While tenuazonic acid itself occurs as a non-crystallizable gum, the crystal structure of its copper salt has previously been reported (Dippenaar et al., 1977). For exemplary crystal structures of other 2,4-dinitrophenylhydrazones see Tameem et al., 2006, Monfared et al., 2007, Valente et al., 2008, Yin et al., 2008. The structure of the title compound is of particular interest, since solubilized tetramic acids and their hydrazones display a variety of tautomeric forms (Yamaguchi et al., 1976a,b, Nolte et al., 1980, Gelin et al., 1982, Royles, 1995, Siegel et al., 2009) (see Fig. 1). While the two rotameric groups I—II and III-IV (Fig. 1) may be differentiated using 1H-NMR, the tautomeric equilibria which are fast on the NMR timescale can not be characterized like that. Furthermore, although common NMR experiments allow for the differentiation of the two rotameric tautomers, the structural assignment of the predominant species is not possible. The presented crystal structure indicates that a six-membered ring involving an intramolecular hydrogen bond between the O5 and N4 is in fact favoured for this compound. On the basis of the presented crystal structure, it can also be assumed, that the thermodynamically favoured tautomer does not involve a double bond of N3 or N4 and thus is tautomer I (Fig. 1). Six N—H···O hydrogen bonds connect each molecule to four adjacent molecules, which are all screw images and span a length of four unit cells. As depicted in Fig. 3 these interactions result in indefinite chains along the b axis.

Related literature top

For the use of the title compound in instrumental analytical chemistry, see: Siegel et al. (2009). For the crystal structure of the tenuazonic copper(II) salt, see: Dippenaar et al. (1977). For the structures of other 2,4-dinitrophenylhydrazones, see: Tameem et al. (2006); Monfared et al. (2007); Valente et al. (2008); Yin et al. (2008). Solubilized tetramic acids and their hydrazones display a variety of tautomeric forms, see: Gelin et al. (1982); Nolte et al. (1980); Royles (1995); Yamaguchi et al. (1976a, 1976b). For the synthesis, see: Lebrun et al. (1988).

Experimental top

The tenuazonic acid natrium salt was supplied by the workgroup of Professor R. Faust (University of Kassel, Germany) by total synthesis from L-isoleucine according to a literature procedure (Lebrun et al., 1988). The title compound was synthesized by adding the tenuazonic acid natrium salt (1 eq.) to a 15 mM solution of 2,4-dinitrophenylhydrazine in 2 N HCl (2 eq.). After 30 minutes of shaking the precipitate was collected, washed with water, dissolved in ethyl acetate and dried with natrium sulfate. After evaporation of the solvent, a yellow powder was obtained, which was recrystallized from ethanol five times to obtain the title compound in analytical purity. For X-ray analysis yellow crystals of tenuazonic acid 2,4-dinitrophenylhydrazone were grown by solvent evaporation from ethanol at ambient temperature over a period of three weeks.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: CORINC (Dräger & Gattow, 1971); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Tautomeric equilibria of tetramic acid dinitrophenylhydrazones.
	Fig. 2. ORTEP representation of the title compound with atomic labeling, shown with 50% probability displacement ellipsoids.
	Fig. 3. View of the crystal packing of the title compound, projected down c. Infinite one-dimensional chains along the [010] direction are formed via strong hydrogen-bonding interactions (indicated by green dashed lines). The intramolecular hydrogen bonds and the isobutyl groups are omitted for clarity.

3-{1-[(2,4-Dinitrophenyl)hydrazino]ethylidene}-5-(1-methylpropyl)pyrrolidine- 2,4-dione top

Crystal data top

C₁₆H₁₉N₅O₆	F(000) = 396
M_r = 377.36	D_x = 1.480 Mg m⁻³
Monoclinic, P2₁	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2yb	Cell parameters from 25 reflections
a = 10.671 (1) Å	θ = 60–69°
b = 4.9387 (5) Å	µ = 0.98 mm⁻¹
c = 16.839 (2) Å	T = 193 K
β = 107.363 (4)°	Needles, yellow
V = 846.98 (15) Å³	0.64 × 0.06 × 0.06 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	3103 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.025
Graphite monochromator	θ_max = 73.6°, θ_min = 2.8°
ω/2θ scans	h = −13→13
Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971)	k = −5→6
T_min = 0.78, T_max = 0.94	l = −20→20
3890 measured reflections	3 standard reflections every 60 min
3282 independent reflections	intensity decay: 2%

Refinement top

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)] = 0.039	H-atom parameters constrained
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0778P)² + 0.1634P] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max < 0.001
3282 reflections	Δρ_max = 0.24 e Å⁻³
247 parameters	Δρ_min = −0.21 e Å⁻³
1 restraint	Absolute structure: (Flack,1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.1 (2)

Crystal data top

C₁₆H₁₉N₅O₆	V = 846.98 (15) Å³
M_r = 377.36	Z = 2
Monoclinic, P2₁	Cu Kα radiation
a = 10.671 (1) Å	µ = 0.98 mm⁻¹
b = 4.9387 (5) Å	T = 193 K
c = 16.839 (2) Å	0.64 × 0.06 × 0.06 mm
β = 107.363 (4)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	3103 reflections with I > 2σ(I)
Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971)	R_int = 0.025
T_min = 0.78, T_max = 0.94	3 standard reflections every 60 min
3890 measured reflections	intensity decay: 2%
3282 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.111	Δρ_max = 0.24 e Å⁻³
S = 0.99	Δρ_min = −0.21 e Å⁻³
3282 reflections	Absolute structure: (Flack,1983)
247 parameters	Absolute structure parameter: 0.1 (2)
1 restraint

Special details top

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) top

	x	y	z	U_iso*/U_eq
O1	0.28853 (17)	1.4445 (4)	0.18665 (10)	0.0394 (4)
O2	0.38017 (15)	1.3663 (4)	0.31656 (10)	0.0373 (4)
O3	−0.1297 (2)	0.5644 (5)	0.06973 (11)	0.0559 (5)
O4	−0.07342 (18)	0.9300 (4)	0.01932 (9)	0.0444 (4)
O5	0.43857 (13)	0.4033 (3)	0.54411 (8)	0.0277 (3)
O6	0.13063 (14)	0.7678 (4)	0.66874 (9)	0.0348 (4)
N1	0.29520 (16)	1.3174 (4)	0.24909 (10)	0.0267 (4)
N2	−0.06562 (18)	0.7738 (4)	0.07614 (11)	0.0339 (4)
N3	0.27686 (16)	1.0106 (4)	0.39501 (10)	0.0280 (4)
H3N	0.3538	1.1087	0.4007	0.034*
N4	0.29331 (16)	0.8153 (4)	0.45682 (10)	0.0266 (4)
H4N	0.3584	0.6959	0.4627	0.032*
N5	0.39181 (16)	0.3303 (4)	0.66688 (9)	0.0262 (4)
H5N	0.4542	0.2158	0.6856	0.031*
C1	0.20134 (18)	1.0983 (4)	0.24520 (12)	0.0230 (4)
C2	0.11472 (18)	1.0434 (4)	0.16609 (11)	0.0254 (4)
H2	0.1175	1.1462	0.1190	0.030*
C3	0.02556 (19)	0.8361 (5)	0.15868 (12)	0.0265 (4)
C4	0.01923 (18)	0.6831 (4)	0.22646 (12)	0.0271 (4)
H4	−0.0428	0.5404	0.2195	0.032*
C5	0.10350 (19)	0.7399 (4)	0.30371 (12)	0.0266 (4)
H5	0.0984	0.6356	0.3500	0.032*
C6	0.19821 (17)	0.9503 (4)	0.31639 (11)	0.0240 (4)
C7	0.23382 (17)	0.8356 (4)	0.51605 (11)	0.0231 (4)
C8	0.27239 (16)	0.6612 (4)	0.58383 (11)	0.0221 (4)
C9	0.37640 (18)	0.4572 (4)	0.59406 (11)	0.0212 (4)
C10	0.30819 (18)	0.4349 (4)	0.71460 (11)	0.0242 (4)
H10	0.2515	0.2860	0.7250	0.029*
C11	0.22234 (17)	0.6447 (4)	0.65454 (11)	0.0246 (4)
C12	0.38790 (18)	0.5633 (4)	0.79844 (11)	0.0253 (4)
H12	0.4282	0.7347	0.7860	0.030*
C13	0.4990 (3)	0.3758 (6)	0.84642 (14)	0.0444 (6)
H13A	0.4600	0.2030	0.8572	0.053*
H13B	0.5552	0.3350	0.8106	0.053*
C14	0.5849 (3)	0.4865 (7)	0.92845 (14)	0.0501 (7)
H14A	0.5337	0.4985	0.9680	0.075*
H14B	0.6165	0.6671	0.9197	0.075*
H14C	0.6599	0.3656	0.9508	0.075*
C15	0.2971 (2)	0.6350 (9)	0.84970 (15)	0.0578 (9)
H15A	0.3448	0.7459	0.8974	0.087*
H15B	0.2664	0.4686	0.8696	0.087*
H15C	0.2216	0.7368	0.8152	0.087*
C16	0.12597 (18)	1.0397 (4)	0.50566 (12)	0.0278 (4)
H16A	0.0503	0.9865	0.4589	0.042*
H16B	0.1572	1.2181	0.4945	0.042*
H16C	0.0999	1.0476	0.5567	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0475 (9)	0.0367 (10)	0.0360 (8)	−0.0111 (7)	0.0159 (7)	0.0053 (7)
O2	0.0333 (7)	0.0348 (9)	0.0376 (7)	−0.0119 (7)	0.0012 (6)	0.0042 (7)
O3	0.0587 (11)	0.0619 (14)	0.0401 (9)	−0.0337 (11)	0.0039 (8)	−0.0078 (9)
O4	0.0529 (9)	0.0479 (11)	0.0256 (7)	−0.0039 (9)	0.0015 (6)	0.0023 (8)
O5	0.0263 (6)	0.0311 (8)	0.0265 (6)	0.0058 (6)	0.0092 (5)	−0.0005 (6)
O6	0.0290 (7)	0.0447 (10)	0.0320 (7)	0.0120 (7)	0.0111 (5)	−0.0006 (7)
N1	0.0266 (8)	0.0226 (9)	0.0316 (8)	−0.0008 (7)	0.0099 (6)	0.0016 (7)
N2	0.0334 (9)	0.0378 (12)	0.0279 (8)	−0.0041 (8)	0.0053 (7)	−0.0050 (8)
N3	0.0256 (7)	0.0300 (10)	0.0246 (8)	−0.0046 (7)	0.0020 (6)	0.0053 (7)
N4	0.0250 (7)	0.0276 (9)	0.0260 (8)	0.0049 (7)	0.0059 (6)	0.0050 (7)
N5	0.0311 (8)	0.0242 (9)	0.0226 (7)	0.0071 (7)	0.0073 (6)	0.0004 (6)
C1	0.0219 (8)	0.0195 (10)	0.0277 (9)	0.0018 (7)	0.0075 (7)	0.0015 (7)
C2	0.0262 (9)	0.0244 (10)	0.0257 (9)	0.0029 (8)	0.0082 (7)	0.0012 (8)
C3	0.0236 (8)	0.0290 (11)	0.0257 (9)	0.0016 (8)	0.0053 (7)	−0.0028 (8)
C4	0.0239 (9)	0.0249 (11)	0.0336 (9)	−0.0028 (8)	0.0104 (7)	−0.0028 (8)
C5	0.0280 (9)	0.0253 (11)	0.0276 (9)	−0.0003 (8)	0.0099 (7)	0.0031 (8)
C6	0.0210 (8)	0.0254 (11)	0.0254 (8)	0.0021 (7)	0.0064 (7)	−0.0011 (8)
C7	0.0204 (8)	0.0213 (9)	0.0239 (8)	−0.0048 (7)	0.0009 (6)	−0.0041 (7)
C8	0.0200 (8)	0.0209 (10)	0.0228 (8)	0.0004 (7)	0.0025 (6)	−0.0032 (7)
C9	0.0218 (8)	0.0175 (10)	0.0221 (8)	−0.0014 (7)	0.0030 (6)	−0.0026 (7)
C10	0.0254 (8)	0.0240 (10)	0.0237 (8)	−0.0011 (8)	0.0083 (7)	−0.0014 (8)
C11	0.0206 (8)	0.0266 (11)	0.0244 (8)	−0.0004 (8)	0.0031 (6)	−0.0037 (8)
C12	0.0274 (9)	0.0266 (11)	0.0209 (8)	0.0008 (8)	0.0056 (7)	−0.0016 (7)
C13	0.0492 (13)	0.0449 (16)	0.0314 (10)	0.0177 (12)	0.0005 (9)	0.0001 (10)
C14	0.0420 (13)	0.071 (2)	0.0305 (11)	0.0011 (13)	−0.0001 (9)	0.0054 (12)
C15	0.0391 (12)	0.102 (3)	0.0311 (11)	0.0168 (15)	0.0088 (9)	−0.0188 (14)
C16	0.0229 (8)	0.0242 (11)	0.0330 (10)	0.0017 (8)	0.0032 (7)	0.0003 (8)

Geometric parameters (Å, º) top

O1—N1	1.208 (2)	C5—H5	0.9500
O2—N1	1.248 (2)	C7—C8	1.391 (3)
O3—N2	1.227 (3)	C7—C16	1.500 (3)
O4—N2	1.212 (3)	C8—C11	1.445 (3)
O5—C9	1.246 (2)	C8—C9	1.470 (3)
O6—C11	1.235 (2)	C10—C11	1.544 (3)
N1—C1	1.463 (3)	C10—C12	1.550 (2)
N2—C3	1.472 (2)	C10—H10	1.0000
N3—C6	1.372 (2)	C12—C15	1.519 (3)
N3—N4	1.391 (2)	C12—C13	1.531 (3)
N3—H3N	0.9328	C12—H12	1.0000
N4—C7	1.336 (2)	C13—C14	1.514 (3)
N4—H4N	0.8942	C13—H13A	0.9900
N5—C9	1.343 (2)	C13—H13B	0.9900
N5—C10	1.462 (2)	C14—H14A	0.9800
N5—H5N	0.8585	C14—H14B	0.9800
C1—C2	1.403 (3)	C14—H14C	0.9800
C1—C6	1.413 (3)	C15—H15A	0.9800
C2—C3	1.378 (3)	C15—H15B	0.9800
C2—H2	0.9500	C15—H15C	0.9800
C3—C4	1.387 (3)	C16—H16A	0.9800
C4—C5	1.372 (3)	C16—H16B	0.9800
C4—H4	0.9500	C16—H16C	0.9800
C5—C6	1.421 (3)

O1—N1—O2	121.99 (18)	N5—C9—C8	108.01 (16)
O1—N1—C1	118.93 (16)	N5—C10—C11	102.55 (14)
O2—N1—C1	119.08 (16)	N5—C10—C12	112.72 (16)
O4—N2—O3	124.19 (18)	C11—C10—C12	112.29 (17)
O4—N2—C3	118.86 (19)	N5—C10—H10	109.7
O3—N2—C3	116.95 (19)	C11—C10—H10	109.7
C6—N3—N4	118.40 (17)	C12—C10—H10	109.7
C6—N3—H3N	118.5	O6—C11—C8	129.87 (19)
N4—N3—H3N	111.9	O6—C11—C10	123.60 (17)
C7—N4—N3	121.63 (17)	C8—C11—C10	106.53 (16)
C7—N4—H4N	119.6	C15—C12—C13	111.46 (19)
N3—N4—H4N	117.4	C15—C12—C10	110.08 (17)
C9—N5—C10	114.12 (17)	C13—C12—C10	111.18 (18)
C9—N5—H5N	120.9	C15—C12—H12	108.0
C10—N5—H5N	124.4	C13—C12—H12	108.0
C2—C1—C6	122.02 (18)	C10—C12—H12	108.0
C2—C1—N1	115.71 (16)	C14—C13—C12	115.2 (2)
C6—C1—N1	122.27 (16)	C14—C13—H13A	108.5
C3—C2—C1	118.11 (18)	C12—C13—H13A	108.5
C3—C2—H2	120.9	C14—C13—H13B	108.5
C1—C2—H2	120.9	C12—C13—H13B	108.5
C2—C3—C4	122.15 (17)	H13A—C13—H13B	107.5
C2—C3—N2	119.00 (18)	C13—C14—H14A	109.5
C4—C3—N2	118.85 (19)	C13—C14—H14B	109.5
C5—C4—C3	119.32 (19)	H14A—C14—H14B	109.5
C5—C4—H4	120.3	C13—C14—H14C	109.5
C3—C4—H4	120.3	H14A—C14—H14C	109.5
C4—C5—C6	121.87 (18)	H14B—C14—H14C	109.5
C4—C5—H5	119.1	C12—C15—H15A	109.5
C6—C5—H5	119.1	C12—C15—H15B	109.5
N3—C6—C1	122.96 (18)	H15A—C15—H15B	109.5
N3—C6—C5	120.45 (17)	C12—C15—H15C	109.5
C1—C6—C5	116.52 (17)	H15A—C15—H15C	109.5
N4—C7—C8	118.42 (17)	H15B—C15—H15C	109.5
N4—C7—C16	118.82 (17)	C7—C16—H16A	109.5
C8—C7—C16	122.73 (17)	C7—C16—H16B	109.5
C7—C8—C11	128.27 (17)	H16A—C16—H16B	109.5
C7—C8—C9	123.28 (16)	C7—C16—H16C	109.5
C11—C8—C9	108.45 (16)	H16A—C16—H16C	109.5
O5—C9—N5	124.91 (18)	H16B—C16—H16C	109.5
O5—C9—C8	127.06 (17)

C6—N3—N4—C7	−105.2 (2)	N4—C7—C8—C11	−179.71 (18)
O1—N1—C1—C2	3.8 (3)	C16—C7—C8—C11	−1.4 (3)
O2—N1—C1—C2	−175.79 (18)	N4—C7—C8—C9	0.7 (3)
O1—N1—C1—C6	−176.46 (19)	C16—C7—C8—C9	178.93 (17)
O2—N1—C1—C6	4.0 (3)	C10—N5—C9—O5	179.12 (18)
C6—C1—C2—C3	−0.8 (3)	C10—N5—C9—C8	−2.4 (2)
N1—C1—C2—C3	179.01 (17)	C7—C8—C9—O5	−3.5 (3)
C1—C2—C3—C4	0.1 (3)	C11—C8—C9—O5	176.79 (19)
C1—C2—C3—N2	−179.57 (18)	C7—C8—C9—N5	178.00 (18)
O4—N2—C3—C2	−10.8 (3)	C11—C8—C9—N5	−1.7 (2)
O3—N2—C3—C2	169.4 (2)	C9—N5—C10—C11	5.1 (2)
O4—N2—C3—C4	169.5 (2)	C9—N5—C10—C12	−115.88 (19)
O3—N2—C3—C4	−10.3 (3)	C7—C8—C11—O6	4.6 (4)
C2—C3—C4—C5	0.5 (3)	C9—C8—C11—O6	−175.7 (2)
N2—C3—C4—C5	−179.82 (18)	C7—C8—C11—C10	−174.97 (18)
C3—C4—C5—C6	−0.5 (3)	C9—C8—C11—C10	4.7 (2)
N4—N3—C6—C1	−162.77 (18)	N5—C10—C11—O6	174.63 (19)
N4—N3—C6—C5	20.5 (3)	C12—C10—C11—O6	−64.1 (2)
C2—C1—C6—N3	−176.16 (18)	N5—C10—C11—C8	−5.7 (2)
N1—C1—C6—N3	4.1 (3)	C12—C10—C11—C8	115.53 (17)
C2—C1—C6—C5	0.7 (3)	N5—C10—C12—C15	−172.8 (2)
N1—C1—C6—C5	−179.02 (17)	C11—C10—C12—C15	72.0 (3)
C4—C5—C6—N3	176.88 (19)	N5—C10—C12—C13	−48.8 (2)
C4—C5—C6—C1	−0.1 (3)	C11—C10—C12—C13	−164.01 (19)
N3—N4—C7—C8	−168.70 (16)	C15—C12—C13—C14	−58.2 (3)
N3—N4—C7—C16	13.0 (3)	C10—C12—C13—C14	178.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O2	0.93	1.99	2.630 (2)	125
N4—H4N···O5	0.89	2.00	2.710 (2)	135
N3—H3N···O5ⁱ	0.93	2.36	2.949 (2)	121
N4—H4N···O5ⁱ	0.89	2.43	2.898 (2)	113
N5—H5N···O2ⁱⁱ	0.86	2.48	3.293 (2)	159

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₉N₅O₆
M_r	377.36
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	193
a, b, c (Å)	10.671 (1), 4.9387 (5), 16.839 (2)
β (°)	107.363 (4)
V (Å³)	846.98 (15)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	0.98
Crystal size (mm)	0.64 × 0.06 × 0.06

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (CORINC; Dräger & Gattow, 1971)
T_min, T_max	0.78, 0.94
No. of measured, independent and observed [I > 2σ(I)] reflections	3890, 3282, 3103
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.622

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.111, 0.99
No. of reflections	3282
No. of parameters	247
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.21
Absolute structure	(Flack,1983)
Absolute structure parameter	0.1 (2)

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), CORINC (Dräger & Gattow, 1971), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O2	0.93	1.99	2.630 (2)	125
N4—H4N···O5	0.89	2.00	2.710 (2)	135
N3—H3N···O5ⁱ	0.93	2.36	2.949 (2)	121
N4—H4N···O5ⁱ	0.89	2.43	2.898 (2)	113
N5—H5N···O2ⁱⁱ	0.86	2.48	3.293 (2)	159

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

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Dippenaar, A., Holzapfel, C. W. & Boeyens, J. C. A. (1977). J. Chem. Crystallogr. 7, 189–197. CAS Google Scholar
Dräger, M. & Gattow, G. (1971). Acta Chem. Scand. 25, 761–762. Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
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Lebrun, M. H., Nicolas, L., Boutar, M., Gaudemer, F., Ranomenjanahary, S. & Gaudemer, A. (1988). Phytochemistry, 27, 77–84. CrossRef CAS Web of Science Google Scholar
Monfared, H. H., Pouralimardan, O. & Janiak, C. (2007). Z. Naturforsch. Teil B, 62, 717–720. Google Scholar
Nolte, M. J., Steyn, P. S. & Wessels, P. L. (1980). J. Chem. Soc. Perkin Trans. 1, pp. 1057–1065. CSD CrossRef Web of Science Google Scholar
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Tameem, A. A., Salhin, A., Saad, B., Rahman, I. A., Saleh, M. I., Ng, S.-L. & Fun, H.-K. (2006). Acta Cryst. E62, o5686–o5688. Web of Science CSD CrossRef IUCr Journals Google Scholar
Valente, E. J., Pawar, D. M., Fronczek, F. R. & Noe, E. A. (2008). Acta Cryst. C64, o447–o449. Web of Science CSD CrossRef IUCr Journals Google Scholar
Yamaguchi, T., Saito, K., Tsujimoto, T. & Yuki, H. (1976a). Bull. Chem. Soc. Jpn, 49, 1161–1162. CrossRef CAS Web of Science Google Scholar
Yamaguchi, T., Saito, K., Tsujimoto, T. & Yuki, H. (1976b). J. Heterocycl. Chem. 13, 533–537. CrossRef CAS Google Scholar
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Volume 65| Part 5| May 2009| Pages o988-o989

doi:10.1107/S1600536809012458

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

3-{1-[(2,4-Di­nitro­phenyl)hydrazino]­ethyl­­idene}-5-(1-methylpropyl)pyrrolidine-2,4-dione

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Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

3-{1-[(2,4-Dinitrophenyl)hydrazino]ethylidene}-5-(1-methylpropyl)pyrrolidine-2,4-dione