4-((E)-{2-[N-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)carboximido­yl]benzyl­idene}amino)-1,5-dimethyl-2-phenyl-2,3-dihydro-1H-pyrazol-3-one

Kim Potgieter; Eric Hosten; Thomas Gerber; Richard Betz

doi:10.1107/S1600536811039158

. 2011 Sep 30;67(Pt 10):o2785–o2786. doi: 10.1107/S1600536811039158

4-((E)-{2-[N-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)carboximidoyl]benzylidene}amino)-1,5-dimethyl-2-phenyl-2,3-dihydro-1H-pyrazol-3-one

Kim Potgieter ^a, Eric Hosten ^a, Thomas Gerber ^a, Richard Betz ^a,^*

PMCID: PMC3201528 PMID: 22064831

Abstract

The title compound, C₃₀H₂₈N₆O₂, is a symmetric diimine derived from ortho-dibenzaldehyde. Both C=N bonds are (E)-configured. The terminal N-bonded phenyl groups adopt staggered conformations relative to their respective parent heterocycles, the relevant least-squares planes intersect at angles of 32.35 (11) and 38.59 (10)°. In the crystal, C—H⋯O contacts connect the molecules into chains along the b axis and give rise to a C ¹ ₁(14)C ¹ ₁(14) and a R ² ₂(12) pattern on different levels of graph-set analysis. The shortest intercentroid distance between two centroids was found at 4.2074 (11) Å between the two five-membered heterocycles.

Related literature

For the crystal structure of another diimine capable of acting as a chelate ligand, see: Yumata et al. (2011 ▶). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶). For details on puckering analysis, see: Cremer & Pople (1975 ▶). For general information about the chelate effect, see: Gade (1998 ▶).

Experimental

Crystal data

C₃₀H₂₈N₆O₂
M _r = 504.58
Monoclinic,
a = 12.6048 (2) Å
b = 7.3389 (2) Å
c = 14.3877 (3) Å
β = 107.622 (1)°
V = 1268.48 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 200 K
0.33 × 0.15 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
12317 measured reflections
3399 independent reflections
2806 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.079
S = 1.01
3399 reflections
347 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811039158/bh2383sup1.cif

e-67-o2785-sup1.cif^{(25KB, cif)}

Supplementary material file. DOI: 10.1107/S1600536811039158/bh2383Isup2.cdx

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811039158/bh2383Isup3.hkl

e-67-o2785-Isup3.hkl^{(166.7KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C45—H45A⋯O2ⁱ	0.98	2.59	3.535 (2)	161
C55—H55A⋯O1ⁱⁱ	0.98	2.61	3.536 (3)	158

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors thank Mr John Robbins for financial and logistical support.

supplementary crystallographic information

Comment

Chelate ligands have found widespread use in coordination chemistry due to the enhanced thermodynamic stability of resultant coordination compounds in relation to metal complexes exclusively applying comparable monodentate ligands (Gade, 1998). In our continuous efforts in elucidating the rules guiding the formation of coordination compounds applying nitrogen-containing chelate ligands, we determined the structure of the title compound to allow for comparative studies in envisioned coordination compounds. Structural information about another diimine capable of acting as a chelate ligand is apparent in the literature (Yumata et al., 2011).

Both C=N double bonds are (E)-configured. The least-squares planes defined by the five-membered heterocycles on the one hand and the central phenyl moiety on the other hand enclose angles of 3.16 (10) and 4.47 (10)°, respectively. The nitrogen-bonded phenyl moieties adopt staggered conformations relative to their respective parent heterocycles, the relevant least-squares planes intersect at angles of 32.35 (11) and 38.59 (10)°. A conformation analysis of the five-membered heterocycles (Cremer & Pople, 1975) is invariably precluded by the small puckering amplitude (Fig. 1).

In the crystal, C–H···O contacts whose range falls by more than 0.1 Å below the sum of van-der-Waals radii are present. These are observed between H atoms of the methyl groups and the ketonic O atoms. In terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995), the descriptor for these interactions is C¹₁(14)C¹₁(14) on the unitary level and emphasizes the presence of two antidromic chains whereas a R²₂(12) descriptor on the binary level highlights the existence of cyclic patterns. In total, the molecules are connected to infinite chains along the crystallographic b axis. The shortest intercentroid distance between two centers of gravity was found at 4.2074 (11) Å (Fig. 2).

The packing of the title compound in the crystal is shown in Figure 3.

Experimental

A solution of 0.99 g of phthalaldehyde in 20 cm³ of methanol was added dropwise to a stirred solution of 3.00 g of 4-aminoantipyrine in 30 cm³ of methanol. The solution was refluxed under nitrogen for 15 minutes. Upon cooling, a yellow precipitate formed which was filtered and dried under reduced pressure. The product was recrystallized from methanol to produce yellow crystals.