Methyl 2-[(E)-(4-nitro­phen­yl)hydrazono]-3-oxobutyrate

The mol­ecule of the title compound, C₁₁H₁₁N₃O₅, exists as the E isomer as it is stabilized by an intra­molecular hydrogen bond. Except for the methyl H atoms, all atoms lie in special positions on a mirror plane and form a large conjugated system; the methyl H atoms are disordered about the mirror plane. In the crystalline state, bifurcated intra- and inter­molecular N—H...O hydrogen bonds and four inter­molecular C—H...O hydrogen bonds link the mol­ecules into large perfectly planar sheets. Along the c axis, the N—N bond center approaches the phenyl-ring centroids of its neighbouring mol­ecules above and below to give π–π overlap (at a distance of ca 3.57 Å), thus fusing the mol­ecules into a three-dimensional framework.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.042
• wR factor = 0.121
• Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C10
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.54
PLAT430_ALERT_2_C Short Inter D...A Contact  O2     ..  O4      ..       2.90 Ang.
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1     ..  O2      ..       2.64 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5     ..  O2      ..       2.62 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4     ..  O4      ..       2.61 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

Phenylhydrazone and its derivatives show remarkable stability and high tendency to form non-centrosymmetric crystal packing (Lewis et al., 1999; Mague et al., 1997) and exceptional electronic, bioactive and chemical properties useful for analytic purposes (Mahy et al., 1993), for biological chemistry (Thami et al., 1992) and also for optical materials (Serbutoviez et al., 1995). As a part of our ongoing research (Liu et al., 2007; Liu et al., 2008), the crystal structure of the title compound was solved.

The molecule of the title compound exists in the (E)-isomer configuration, not as the generally more stable (Z)-isomer (Schemes 1 and 2). The (E)-isomer exists here because of the N—H···O intra-molecular hydrogen bond stabilizes it by forming a pseudo-ring S(6) (Bernstein et al., 1995) motif (Fig. 1, Table 1 and 2). The N1—C6 bond distance at 1.397 (3) Å is longer than the expected C═N double bond (1.32 Å) but is shorter than a C—N single bond (1.47 Å) because of the classic sp²-hybrid nitrogen atom, as also found in our earlier work (Liu et al., 2007, 2008). All these effects may help all non-hydrogen atoms to form a perfect plane which coincides with the mirror plane of the space group, less for the hydrogen atoms of the two methyl groups whose six H atoms are disordered over two orientations.

In the crystal packing the molecules are linked into larger perfectly planar sheets via by four C—H···O inter-molecular hydrogen bonds and one N—H···O intra-molecular hydrogen bond running parallel to the [001] plane (Fig. 2, Table 2). H1 atom of the N1 atom is a part of a bifurcated system and makes both intra- and intermolecular H-bridges, with angles around the H1 adding up to 360°. Finally, along the c axis the N1—N2 bond centers of molecules combine its up and down neighbours' phenyl rings into three dimensional framework (Fig. 2). Consecutive bond centers···phenyl ring centers are at a distance of ca. 3.57 Å and an incline at an angle of ca. 137° (Fig. 3).

Related literature

For related literature, see: Bernstein et al. (1995); Lewis et al. (1999); Liu et al. (2007, 2008); Mague et al. (1997); Mahy et al. (1993); Serbutoviez et al. (1995); Thami et al. (1992); Wang et al. (2005).

S2. Experimental

The title compound was synthesized according to literature procedure (Wang et al. 2005; Liu et al. 2008). Crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution of the solid in dichloromethane at room temperature over a period of 6 d.

S3. Refinement

After their location in a difference map, all H atoms were fixed geometrically at ideal positions and allowed to ride on the parent C atoms, with C—H distances of 0.93 (aromatic) or 0.97 Å (methyl), and with U_iso(H) values of 1.2U_eq (C, N).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids. Disorder of the two methyl groups are indicated and the N–H···O intra-molecular hydrogen bond shown as dashed lines.
	Fig. 2. Part of the crystal structure of the title compound, showing the formation of a hydrogen bonded plane parallel to [001], which is built by one N—H···O and four C—H···O inter-molecular hydrogen bonds (dashed lines). For the sake of clarity, H atoms not involved in hydrogen bonding have been omitted.
	Fig. 3. Excerpt of the crystal structure of the title compound, showing that along the c axis the N1—N2 bond center of one molecule combines its up and down phenyl rings in the other two molecules into a three dimensional framework. H atoms not involved in hydrogen bonding have been omitted.
	Fig. 4. The E and Z isomers of the title compound.

(Z)-3-Ferrocenyl-2-(4-pyridyl)propenenitrile

Crystal data

C11H11N3O5	Dx = 1.442 Mg m^−3
Mr = 265.2	Melting point: 400 K
Orthorhombic, Pbcm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2c 2b	Cell parameters from 1996 reflections
a = 12.880 (3) Å	θ = 2.8–25.4°
b = 14.299 (3) Å	µ = 0.12 mm^−1
c = 6.6328 (14) Å	T = 296 K
V = 1221.6 (5) Å^3	Block, yellow
Z = 4	0.30 × 0.30 × 0.20 mm
F(000) = 552

Data collection

Bruker SMART 1000 CCD diffractometer	1546 independent reflections
Radiation source: fine-focus sealed tube	968 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
Thin–slice ω scans	θmax = 27.6°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −16→16
Tmin = 0.966, Tmax = 0.977	k = −17→18
10245 measured reflections	l = −8→8

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.121	w = 1/[σ^2(Fo^2) + (0.0497P)^2 + 0.2977P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
1546 reflections	Δρmax = 0.20 e Å^−3
118 parameters	Δρmin = −0.13 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0036 (9)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O4	0.68298 (15)	0.51128 (12)	0.2500	0.0726 (6)
O3	1.00596 (16)	0.52888 (14)	0.2500	0.0896 (8)
O1	0.68240 (17)	−0.10594 (13)	0.2500	0.0887 (8)
O2	0.52310 (17)	−0.06963 (13)	0.2500	0.1081 (10)
N3	0.61352 (18)	−0.04820 (14)	0.2500	0.0582 (6)
N1	0.72021 (14)	0.33126 (12)	0.2500	0.0422 (5)
H1	0.6721	0.3730	0.2500	0.051*
N2	0.81817 (14)	0.35582 (13)	0.2500	0.0435 (5)
C10	0.7757 (2)	0.52229 (16)	0.2500	0.0489 (6)
C6	0.69506 (16)	0.23623 (15)	0.2500	0.0379 (5)
C8	0.9648 (2)	0.45339 (18)	0.2500	0.0597 (7)
C5	0.59053 (17)	0.21060 (14)	0.2500	0.0436 (6)
H5	0.5392	0.2563	0.2500	0.052*
C2	0.74469 (18)	0.07505 (15)	0.2500	0.0447 (6)
H2	0.7957	0.0290	0.2500	0.054*
C4	0.56352 (18)	0.11723 (15)	0.2500	0.0475 (6)
H4	0.4941	0.0993	0.2500	0.057*
O5	0.81917 (15)	0.60575 (12)	0.2500	0.0768 (7)
C3	0.64146 (18)	0.05094 (15)	0.2500	0.0423 (5)
C1	0.77167 (17)	0.16807 (15)	0.2500	0.0431 (6)
H1A	0.8413	0.1853	0.2500	0.052*
C9	0.84922 (18)	0.44293 (16)	0.2500	0.0453 (6)
C7	1.0288 (2)	0.3663 (2)	0.2500	0.0906 (12)
H7A	1.0318	0.3412	0.1158	0.136*	0.50
H7B	0.9980	0.3211	0.3387	0.136*	0.50
H7C	1.0978	0.3806	0.2954	0.136*	0.50
C11	0.7477 (3)	0.68338 (19)	0.2500	0.0908 (11)
H11A	0.7153	0.6882	0.1201	0.136*	0.50
H11B	0.7847	0.7401	0.2788	0.136*	0.50
H11C	0.6955	0.6735	0.3511	0.136*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O4	0.0474 (12)	0.0424 (10)	0.1281 (19)	−0.0013 (8)	0.000	0.000
O3	0.0517 (12)	0.0553 (13)	0.162 (2)	−0.0184 (10)	0.000	0.000
O1	0.0783 (14)	0.0355 (10)	0.152 (2)	0.0124 (10)	0.000	0.000
O2	0.0591 (13)	0.0402 (11)	0.225 (3)	−0.0140 (10)	0.000	0.000
N3	0.0587 (14)	0.0335 (11)	0.0824 (16)	−0.0003 (11)	0.000	0.000
N1	0.0398 (10)	0.0318 (10)	0.0551 (12)	−0.0030 (8)	0.000	0.000
N2	0.0430 (11)	0.0392 (10)	0.0482 (12)	−0.0067 (9)	0.000	0.000
C10	0.0524 (16)	0.0355 (13)	0.0588 (16)	−0.0074 (11)	0.000	0.000
C6	0.0426 (12)	0.0333 (11)	0.0377 (12)	−0.0018 (10)	0.000	0.000
C8	0.0493 (15)	0.0478 (15)	0.0821 (19)	−0.0102 (13)	0.000	0.000
C5	0.0417 (12)	0.0317 (12)	0.0575 (14)	0.0039 (9)	0.000	0.000
C2	0.0434 (13)	0.0358 (12)	0.0547 (14)	0.0065 (10)	0.000	0.000
C4	0.0392 (12)	0.0369 (12)	0.0664 (16)	−0.0023 (10)	0.000	0.000
O5	0.0622 (12)	0.0348 (10)	0.1333 (19)	−0.0092 (9)	0.000	0.000
C3	0.0456 (13)	0.0283 (11)	0.0530 (14)	0.0000 (10)	0.000	0.000
C1	0.0381 (12)	0.0404 (13)	0.0507 (14)	−0.0020 (10)	0.000	0.000
C9	0.0460 (13)	0.0360 (12)	0.0537 (14)	−0.0081 (10)	0.000	0.000
C7	0.0511 (17)	0.0568 (17)	0.164 (4)	−0.0011 (14)	0.000	0.000
C11	0.088 (2)	0.0336 (14)	0.150 (3)	−0.0002 (16)	0.000	0.000

Geometric parameters (Å, º)

O4—C10	1.204 (3)	C5—C4	1.380 (3)
O3—C8	1.203 (3)	C5—H5	0.9300
O1—N3	1.212 (3)	C2—C3	1.374 (3)
O2—N3	1.204 (3)	C2—C1	1.375 (3)
N3—C3	1.463 (3)	C2—H2	0.9300
N1—N2	1.310 (2)	C4—C3	1.381 (3)
N1—C6	1.397 (3)	C4—H4	0.9300
N1—H1	0.8600	O5—C11	1.442 (3)
N2—C9	1.308 (3)	C1—H1A	0.9300
C10—O5	1.318 (3)	C7—H7A	0.9600
C10—C9	1.478 (3)	C7—H7B	0.9600
C6—C1	1.387 (3)	C7—H7C	0.9600
C6—C5	1.395 (3)	C11—H11A	0.9600
C8—C7	1.494 (4)	C11—H11B	0.9600
C8—C9	1.496 (3)	C11—H11C	0.9600
O2—N3—O1	122.3 (2)	C3—C4—H4	120.6
O2—N3—C3	119.0 (2)	C10—O5—C11	115.2 (2)
O1—N3—C3	118.7 (2)	C2—C3—C4	122.1 (2)
N2—N1—C6	118.96 (18)	C2—C3—N3	118.8 (2)
N2—N1—H1	120.5	C4—C3—N3	119.1 (2)
C6—N1—H1	120.5	C2—C1—C6	120.0 (2)
C9—N2—N1	123.4 (2)	C2—C1—H1A	120.0
O4—C10—O5	122.7 (2)	C6—C1—H1A	120.0
O4—C10—C9	122.3 (2)	N2—C9—C10	122.4 (2)
O5—C10—C9	115.0 (2)	N2—C9—C8	113.5 (2)
C1—C6—C5	120.1 (2)	C10—C9—C8	124.1 (2)
C1—C6—N1	121.24 (19)	C8—C7—H7A	109.5
C5—C6—N1	118.64 (19)	C8—C7—H7B	109.5
O3—C8—C7	120.3 (2)	H7A—C7—H7B	109.5
O3—C8—C9	121.9 (2)	C8—C7—H7C	109.5
C7—C8—C9	117.8 (2)	H7A—C7—H7C	109.5
C4—C5—C6	119.8 (2)	H7B—C7—H7C	109.5
C4—C5—H5	120.1	O5—C11—H11A	109.5
C6—C5—H5	120.1	O5—C11—H11B	109.5
C3—C2—C1	119.2 (2)	H11A—C11—H11B	109.5
C3—C2—H2	120.4	O5—C11—H11C	109.5
C1—C2—H2	120.4	H11A—C11—H11C	109.5
C5—C4—C3	118.8 (2)	H11B—C11—H11C	109.5
C5—C4—H4	120.6
C6—N1—N2—C9	180.0	O1—N3—C3—C4	180.0
N2—N1—C6—C1	0.0	C3—C2—C1—C6	0.0
N2—N1—C6—C5	180.0	C5—C6—C1—C2	0.0
C1—C6—C5—C4	0.0	N1—C6—C1—C2	180.0
N1—C6—C5—C4	180.0	N1—N2—C9—C10	0.0
C6—C5—C4—C3	0.0	N1—N2—C9—C8	180.0
O4—C10—O5—C11	0.0	O4—C10—C9—N2	0.0
C9—C10—O5—C11	180.0	O5—C10—C9—N2	180.0
C1—C2—C3—C4	0.0	O4—C10—C9—C8	180.0
C1—C2—C3—N3	180.0	O5—C10—C9—C8	0.0
C5—C4—C3—C2	0.0	O3—C8—C9—N2	180.0
C5—C4—C3—N3	180.0	C7—C8—C9—N2	0.0
O2—N3—C3—C2	180.0	O3—C8—C9—C10	0.0
O1—N3—C3—C2	0.0	C7—C8—C9—C10	180.0
O2—N3—C3—C4	0.0

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4	0.86	1.98	2.618 (3)	130
C2—H2···O3^i	0.93	2.55	3.279 (3)	135
C11—H11B···O1^ii	0.96	2.57	3.128 (3)	117
N1—H1···O2^iii	0.86	2.64	3.439 (3)	154
C5—H5···O2^iii	0.93	2.62	3.467 (4)	153
C4^iii—H4^iii···O4	0.93	2.61	3.518 (3)	167

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