Diethyl (E)-2,3-bis­[(E)-(2-methyl-2-phenyl­hydrazin-1-yl­idene)meth­yl]but-2-enedioate

Liu, P.; Yuan, L.; Song, X.; Yan, H.

doi:10.1107/S1600536814011970

organic compounds

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Volume 70| Part 6| June 2014| Page o723

doi:10.1107/S1600536814011970

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Diethyl (E)-2,3-bis[(E)-(2-methyl-2-phenylhydrazin-1-ylidene)methyl]but-2-enedioate

Peng Liu,^a Libin Yuan,^a Xiuqing Song ^a and Hong Yan ^a ^*

^aCollege of Life Science and Bio-engineering, Beijing University of Technology, Pingleyuan Street No. 100, Chaoyang District, Beijing 100124, People's Republic of China
^*Correspondence e-mail: hongyan@bjut.edu.cn

(Received 4 May 2014; accepted 22 May 2014; online 31 May 2014)

The complete molecule of the title compound, C₂₄H₂₈N₄O₄, is generated by crystallographic inversion symmetry. The ethyl side chain is disordered over two sets of sites in a 0.57 (4):0.43 (4) ratio. The dihedral angles between the methylidene group and the phenyl ring and ester side chain (major conformation) are 7.61 (8) and 86.95 (8)°, respectively. In the crystal, molecules are linked via C—H⋯O hydrogen bonds, forming corrugated sheets lying parallel to (010).

CCDC reference: 1004694

Related literature

For background to this class of compound, see: Aumann et al. (1987 ). For studies of related molecules, see: Mandal & Basak (2009 ); Woerlee et al. (1984 ).

Experimental

Crystal data

C₂₄H₂₈N₄O₄
M_r = 436.50
Orthorhombic, P b c a
a = 15.922 (3) Å
b = 8.0335 (16) Å
c = 18.655 (4) Å
V = 2386.2 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 113 K
0.20 × 0.10 × 0.08 mm

Data collection

Rigaku Saturn CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.983, T_max = 0.993
14849 measured reflections
2093 independent reflections
1925 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.099
S = 1.08
2093 reflections
168 parameters
40 restraints
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O1ⁱ	0.95	2.47	3.3749 (19)	160
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+2, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 1004694

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814011970/hb7226sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814011970/hb7226Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814011970/hb7226Isup3.cml

checkCIF report

Related literature top

For background to this class of compound, see: Aumann et al. (1987). For studies of related molecules, see: Mandal & Basak (2009); Woerlee et al. (1984).

Experimental top

Ethyl 3-ethoxy-2-nitroacrylate (10.6 mmol) and hydrazine (10.6 mmol) were stirred in ethanol, and the solution was heated briefly to boiling. A yellow solid was collected by filtration after the mixture was left to stand for 24 h. The product was recrystallized from dichloromethane and petroleum ether as red blocks in 31% yield (m.p. 160° C).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Ellipsoid plot with displacement ellipsoids drawn at the 50% probability level.

Diethyl (E)-2,3-bis[(E)-(2-methyl-2-phenylhydrazin-1-ylidene)methyl]but-2-enedioate top

Crystal data top

C₂₄H₂₈N₄O₄	D_x = 1.215 Mg m⁻³
M_r = 436.50	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 6374 reflections
a = 15.922 (3) Å	θ = 2.2–27.9°
b = 8.0335 (16) Å	µ = 0.08 mm⁻¹
c = 18.655 (4) Å	T = 113 K
V = 2386.2 (8) Å³	Block, red
Z = 4	0.20 × 0.10 × 0.08 mm
F(000) = 928

Data collection top

Rigaku Saturn CCD diffractometer	2093 independent reflections
Radiation source: rotating anode	1925 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.034
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.0°, θ_min = 2.5°
ω and ϕ scans	h = −15→18
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −9→9
T_min = 0.983, T_max = 0.993	l = −22→22
14849 measured reflections

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)] = 0.038	H-atom parameters constrained
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0585P)² + 0.373P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2093 reflections	Δρ_max = 0.18 e Å⁻³
168 parameters	Δρ_min = −0.16 e Å⁻³
40 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.063 (4)

Crystal data top

C₂₄H₂₈N₄O₄	V = 2386.2 (8) Å³
M_r = 436.50	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 15.922 (3) Å	µ = 0.08 mm⁻¹
b = 8.0335 (16) Å	T = 113 K
c = 18.655 (4) Å	0.20 × 0.10 × 0.08 mm

Data collection top

Rigaku Saturn CCD diffractometer	2093 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1925 reflections with I > 2σ(I)
T_min = 0.983, T_max = 0.993	R_int = 0.034
14849 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	40 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.08	Δρ_max = 0.18 e Å⁻³
2093 reflections	Δρ_min = −0.16 e Å⁻³
168 parameters

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	Occ. (<1)
O1	0.17130 (5)	0.95435 (11)	0.47833 (5)	0.0331 (3)
O2	0.08700 (5)	0.74716 (11)	0.44282 (5)	0.0363 (3)
N1	0.03970 (6)	1.17222 (12)	0.29214 (5)	0.0269 (3)
N2	0.05365 (6)	1.08830 (12)	0.35347 (5)	0.0240 (3)
C1	0.10279 (7)	1.15535 (14)	0.23935 (6)	0.0258 (3)
C2	0.09073 (9)	1.21349 (17)	0.16961 (7)	0.0365 (3)
H2A	0.0404	1.2705	0.1574	0.044*
C3	0.15209 (11)	1.18797 (19)	0.11824 (7)	0.0468 (4)
H3A	0.1438	1.2298	0.0711	0.056*
C4	0.22471 (10)	1.1034 (2)	0.13400 (8)	0.0484 (4)
H4A	0.2658	1.0845	0.0980	0.058*
C5	0.23704 (9)	1.04608 (18)	0.20314 (7)	0.0416 (4)
H5A	0.2870	0.9872	0.2145	0.050*
C6	0.17769 (8)	1.07337 (16)	0.25580 (7)	0.0315 (3)
H6A	0.1878	1.0363	0.3034	0.038*
C7	−0.03664 (8)	1.26664 (17)	0.28254 (7)	0.0373 (3)
H7A	−0.0408	1.3515	0.3201	0.056*
H7B	−0.0851	1.1917	0.2855	0.056*
H7C	−0.0358	1.3208	0.2355	0.056*
C8	0.00195 (7)	1.09756 (14)	0.40658 (6)	0.0243 (3)
H8A	−0.0473	1.1640	0.4044	0.029*
C9	0.02301 (7)	1.00148 (13)	0.46959 (6)	0.0229 (3)
C10	0.10276 (7)	0.90180 (14)	0.46439 (6)	0.0235 (3)
C11	0.1581 (6)	0.6302 (13)	0.4421 (8)	0.0421 (19)	0.57 (4)
H11A	0.1836	0.6218	0.4904	0.051*	0.57 (4)
H11B	0.2017	0.6679	0.4079	0.051*	0.57 (4)
C12	0.1231 (7)	0.4658 (13)	0.4194 (9)	0.052 (2)	0.57 (4)
H12A	0.1689	0.3854	0.4140	0.078*	0.57 (4)
H12B	0.0938	0.4784	0.3735	0.078*	0.57 (4)
H12C	0.0835	0.4258	0.4558	0.078*	0.57 (4)
C11'	0.1622 (7)	0.6478 (17)	0.4289 (12)	0.045 (3)	0.43 (4)
H11C	0.1926	0.6258	0.4743	0.054*	0.43 (4)
H11D	0.2003	0.7077	0.3959	0.054*	0.43 (4)
C12'	0.1334 (9)	0.4862 (17)	0.3956 (10)	0.048 (2)	0.43 (4)
H12D	0.1802	0.4070	0.3948	0.071*	0.43 (4)
H12E	0.1143	0.5070	0.3465	0.071*	0.43 (4)
H12F	0.0871	0.4399	0.4238	0.071*	0.43 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0242 (5)	0.0348 (5)	0.0403 (5)	−0.0016 (4)	−0.0039 (4)	−0.0055 (4)
O2	0.0245 (5)	0.0250 (5)	0.0593 (6)	0.0043 (4)	−0.0072 (4)	−0.0100 (4)
N1	0.0295 (6)	0.0269 (5)	0.0241 (5)	0.0043 (4)	−0.0007 (4)	0.0049 (4)
N2	0.0276 (6)	0.0224 (5)	0.0221 (5)	0.0000 (4)	−0.0013 (4)	0.0010 (4)
C1	0.0306 (7)	0.0229 (6)	0.0238 (6)	−0.0058 (5)	0.0006 (5)	−0.0013 (4)
C2	0.0445 (8)	0.0366 (7)	0.0283 (7)	−0.0022 (6)	−0.0028 (6)	0.0055 (5)
C3	0.0619 (10)	0.0532 (9)	0.0254 (7)	−0.0081 (8)	0.0061 (7)	0.0062 (6)
C4	0.0516 (10)	0.0571 (9)	0.0366 (7)	−0.0069 (7)	0.0177 (7)	−0.0026 (7)
C5	0.0345 (8)	0.0477 (8)	0.0427 (8)	−0.0009 (6)	0.0099 (6)	−0.0005 (6)
C6	0.0303 (7)	0.0356 (7)	0.0285 (6)	−0.0015 (5)	0.0016 (5)	0.0024 (5)
C7	0.0341 (8)	0.0414 (8)	0.0366 (7)	0.0111 (6)	−0.0008 (6)	0.0104 (6)
C8	0.0237 (6)	0.0228 (6)	0.0263 (6)	0.0015 (5)	−0.0008 (5)	−0.0013 (4)
C9	0.0231 (6)	0.0210 (6)	0.0245 (6)	−0.0014 (5)	−0.0012 (5)	−0.0031 (4)
C10	0.0259 (7)	0.0249 (6)	0.0196 (6)	−0.0001 (5)	−0.0003 (5)	0.0000 (4)
C11	0.027 (2)	0.028 (2)	0.071 (4)	0.0120 (19)	−0.006 (2)	−0.007 (2)
C12	0.045 (3)	0.029 (3)	0.083 (5)	0.010 (2)	−0.012 (3)	−0.015 (3)
C11'	0.032 (3)	0.029 (3)	0.073 (6)	0.008 (2)	−0.005 (3)	−0.016 (3)
C12'	0.037 (3)	0.032 (3)	0.074 (5)	0.006 (2)	0.004 (4)	−0.007 (3)

Geometric parameters (Å, º) top

O1—C10	1.1987 (14)	C7—H7A	0.9800
O2—C10	1.3298 (15)	C7—H7B	0.9800
O2—C11'	1.462 (8)	C7—H7C	0.9800
O2—C11	1.472 (6)	C8—C9	1.4458 (16)
N1—N2	1.3463 (13)	C8—H8A	0.9500
N1—C1	1.4133 (15)	C9—C9ⁱ	1.351 (2)
N1—C7	1.4440 (16)	C9—C10	1.5042 (16)
N2—C8	1.2902 (14)	C11—C12	1.495 (7)
C1—C2	1.3956 (17)	C11—H11A	0.9900
C1—C6	1.3964 (18)	C11—H11B	0.9900
C2—C3	1.384 (2)	C12—H12A	0.9800
C2—H2A	0.9500	C12—H12B	0.9800
C3—C4	1.373 (2)	C12—H12C	0.9800
C3—H3A	0.9500	C11'—C12'	1.511 (8)
C4—C5	1.383 (2)	C11'—H11C	0.9900
C4—H4A	0.9500	C11'—H11D	0.9900
C5—C6	1.3807 (18)	C12'—H12D	0.9800
C5—H5A	0.9500	C12'—H12E	0.9800
C6—H6A	0.9500	C12'—H12F	0.9800

C10—O2—C11'	114.1 (6)	H7A—C7—H7C	109.5
C10—O2—C11	117.0 (5)	H7B—C7—H7C	109.5
C11'—O2—C11	11.4 (12)	N2—C8—C9	116.46 (10)
N2—N1—C1	115.27 (9)	N2—C8—H8A	121.8
N2—N1—C7	120.49 (10)	C9—C8—H8A	121.8
C1—N1—C7	124.21 (10)	C9ⁱ—C9—C8	124.51 (14)
C8—N2—N1	121.22 (10)	C9ⁱ—C9—C10	120.18 (13)
C2—C1—C6	118.71 (11)	C8—C9—C10	115.31 (10)
C2—C1—N1	121.31 (11)	O1—C10—O2	124.51 (11)
C6—C1—N1	119.94 (10)	O1—C10—C9	124.54 (11)
C3—C2—C1	119.92 (13)	O2—C10—C9	110.95 (10)
C3—C2—H2A	120.0	O2—C11—C12	106.2 (7)
C1—C2—H2A	120.0	O2—C11—H11A	110.5
C4—C3—C2	121.30 (13)	C12—C11—H11A	110.5
C4—C3—H3A	119.3	O2—C11—H11B	110.5
C2—C3—H3A	119.3	C12—C11—H11B	110.5
C3—C4—C5	118.93 (13)	H11A—C11—H11B	108.7
C3—C4—H4A	120.5	O2—C11'—C12'	107.1 (10)
C5—C4—H4A	120.5	O2—C11'—H11C	110.3
C6—C5—C4	120.90 (14)	C12'—C11'—H11C	110.3
C6—C5—H5A	119.6	O2—C11'—H11D	110.3
C4—C5—H5A	119.6	C12'—C11'—H11D	110.3
C5—C6—C1	120.20 (12)	H11C—C11'—H11D	108.6
C5—C6—H6A	119.9	C11'—C12'—H12D	109.5
C1—C6—H6A	119.9	C11'—C12'—H12E	109.5
N1—C7—H7A	109.5	H12D—C12'—H12E	109.5
N1—C7—H7B	109.5	C11'—C12'—H12F	109.5
H7A—C7—H7B	109.5	H12D—C12'—H12F	109.5
N1—C7—H7C	109.5	H12E—C12'—H12F	109.5

C1—N1—N2—C8	177.93 (10)	N2—C8—C9—C9ⁱ	178.85 (14)
C7—N1—N2—C8	−4.05 (16)	N2—C8—C9—C10	−0.46 (15)
N2—N1—C1—C2	169.89 (11)	C11'—O2—C10—O1	−6.8 (10)
C7—N1—C1—C2	−8.05 (18)	C11—O2—C10—O1	5.4 (7)
N2—N1—C1—C6	−7.57 (15)	C11'—O2—C10—C9	173.7 (10)
C7—N1—C1—C6	174.49 (12)	C11—O2—C10—C9	−174.1 (7)
C6—C1—C2—C3	0.60 (19)	C9ⁱ—C9—C10—O1	−92.64 (17)
N1—C1—C2—C3	−176.88 (12)	C8—C9—C10—O1	86.70 (14)
C1—C2—C3—C4	1.2 (2)	C9ⁱ—C9—C10—O2	86.85 (16)
C2—C3—C4—C5	−1.4 (2)	C8—C9—C10—O2	−93.81 (12)
C3—C4—C5—C6	−0.2 (2)	C10—O2—C11—C12	177.4 (7)
C4—C5—C6—C1	1.9 (2)	C11'—O2—C11—C12	−104 (6)
C2—C1—C6—C5	−2.13 (18)	C10—O2—C11'—C12'	−172.3 (7)
N1—C1—C6—C5	175.39 (11)	C11—O2—C11'—C12'	81 (5)
N1—N2—C8—C9	179.66 (10)

Symmetry code: (i) −x, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O1ⁱⁱ	0.95	2.47	3.3749 (19)	160

Symmetry code: (ii) −x+1/2, −y+2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O1ⁱ	0.95	2.47	3.3749 (19)	160

Symmetry code: (i) −x+1/2, −y+2, z−1/2.

Acknowledgements

This work was supported financially by the Key Projects in the National Science & Technology Pillar Program (No. 2012ZX10001007–008-002) and the Doctoral Fund of Innovation of Beijing University of Technology.

References

Aumann, R., Kuckert, E. & Heinen, H. (1987). Chem. Ber. 120, 1293–1296. CrossRef CAS Web of Science Google Scholar
Mandal, S. & Basak, A. (2009). Tetrahedron Lett. 50, 3641–3644. Web of Science CrossRef CAS Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Woerlee, E., Bosma, R., Van Eijl, J. & Mol, J. (1984). Appl. Catal. 10, 219–229. CrossRef CAS Web of Science Google Scholar

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Di­ethyl (E)-2,3-bis­­[(E)-(2-methyl-2-phenyl­hydrazin-1-yl­­idene)meth­yl]but-2-enedioate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Diethyl (E)-2,3-bis[(E)-(2-methyl-2-phenylhydrazin-1-ylidene)methyl]but-2-enedioate