N 2,N 2′-Bis(2,2-dimethyl­propano­yl)benzene-1,3-dicarbohydrazide

Hoong-Kun Fun; Suchada Chantrapromma; Subrata Jana; Anita Hazra; Shyamaprosad Goswami

doi:10.1107/S1600536807063210

. 2007 Dec 6;64(Pt 1):o175–o176. doi: 10.1107/S1600536807063210

N ²,N ^2′-Bis(2,2-dimethylpropanoyl)benzene-1,3-dicarbohydrazide

Hoong-Kun Fun ^a,^*, Suchada Chantrapromma ^b,^‡, Subrata Jana ^c, Anita Hazra ^c, Shyamaprosad Goswami ^c

PMCID: PMC2915239 PMID: 21200739

Abstract

In the molecular structure of the title hydrazide derivative, C₁₈H₂₆N₄O₄, the conformations of the two units of 2-(2,2-dimethyl-1-oxopropyl)hydrazide substituents are not planar; these two units are attached axially to the benzene ring with C(ortho)—C—C(=O)—N torsion angles of 28.1 (2) and 31.0 (2)° [where C(ortho) is the C atom at position 4 of the benzene ring relative to the substituent at position 3 or the C atom at position 6 of the benzene ring relative to the substituent at position 1, as appropriate]. The dihedral angles between the hydrazide units and the benzene ring are 62.66 (7) and 63.84 (7)°. In the crystal structure, molecules are arranged in an anti-parallel manner and are linked by N—H⋯O intermolecular hydrogen bonds and weak C—H⋯O intermolecular interactions into a three-dimensional network. The structure is further stabilized by a weak C—H⋯N intramolecular interaction.

Related literature

For values of bond lengths, see: Allen et al. (1987 ▶). For related literature on the applications and bioactivities of hydrazide derivatives, see for example: Feng et al. (2006 ▶); Fernández et al. (2004 ▶); Hołtra et al. (2007 ▶); Imramovský et al. (2007 ▶); Kim et al. (2007 ▶); Lemay et al. (2007 ▶); Liu et al. (2006 ▶); Nica et al. (2007 ▶); Raveendran & Pal (2007 ▶); Rivero & Buchwald (2007 ▶); Sicardi et al. (1980 ▶); Yang et al. (2007 ▶).

Experimental

Crystal data

C₁₈H₂₆N₄O₄
M _r = 362.43
Monoclinic,
a = 7.1853 (2) Å
b = 14.8928 (4) Å
c = 17.1656 (5) Å
β = 96.050 (2)°
V = 1826.65 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100.0 (1) K
0.56 × 0.10 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.949, T _max = 0.993
34290 measured reflections
5301 independent reflections
3858 reflections with I > 2σ(I)
R _int = 0.071

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.141
S = 1.06
5301 reflections
257 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 1998 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807063210/is2255sup1.cif

e-64-0o175-sup1.cif^{(21.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063210/is2255Isup2.hkl

e-64-0o175-Isup2.hkl^{(259.6KB, 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
N1—H1N1⋯O3ⁱ	0.90 (2)	2.12 (2)	3.0193 (16)	176.7 (16)
N2—H1N2⋯O4ⁱⁱ	0.845 (18)	1.993 (19)	2.8262 (17)	169 (2)
N3—H1N3⋯O1ⁱⁱⁱ	0.876 (18)	1.969 (18)	2.8307 (16)	167.3 (16)
N4—H1N4⋯O2^iv	0.878 (19)	2.059 (19)	2.9320 (16)	172.3 (19)
C1—H1A⋯O4ⁱⁱ	0.93	2.48	3.1879 (17)	133
C3—H3A⋯O1ⁱⁱⁱ	0.93	2.56	3.2854 (17)	135
C12—H12C⋯O3ⁱ	0.96	2.52	3.433 (2)	159
C18—H18C⋯N4	0.96	2.61	2.9347 (19)	100

Open in a new tab

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

Acknowledgments

SJ, AH and SG acknowledge the DST [SR/S1/OC-13/2005] and CSIR [01(1913)/04/EMR-II], Government of India, for financial support. SJ and AH thank the CSIR, Government of India, for research fellowships. SC thanks Prince of Songkla University for support. The authors also thank the Malaysian Government and Universiti Sains Malaysia for the Scientific Advancement Grant Allocation (SAGA) grant No. 304/PFIZIK/653003/A118.

supplementary crystallographic information

Comment

Hydrazide derivatives of different compounds are very important units in host–guest chemistry due to their special arrangement of donor-acceptors (Feng et al., 2006; Yang et al., 2007). These types of compounds are also important for the metal coordinations and related studies (Hołtra et al., 2007; Nica et al., 2007; Raveendran & Pal, 2007). Hydrazide-based compounds are also involved in different synthetic applications (Fernández et al., 2004; Lemay et al., 2007; Kim et al., 2007; Rivero & Buchwald, 2007) as well as in medicinal activities (Imramovský et al., 2007; Liu et al., 2006; Sicardi et al., 1980). We synthesized the title compound for being a host of host–guest complexes syntheses. The single-crystal X-ray structural study of the title compound was undertaken in order to establish the three-dimensional structure and to gain more details of conformations of the various groups.

In the molecular structure of the title compound (Fig. 1), the conformations of the two units of 2-(2,2-dimethyl-1-oxopropyl)hydrazide substituents are not planar which can be indicated by the dihedral angles between the mean planes of C6/C7/O2/N2 and O1/N1/N2/C8/C9 = 87.77 (8)° and C4/C13/O3/N3 and O4/N3/N4/C14/C15 = 87.90 (8)°. These two units are axially attached to the benzene ring with the torsion angles C1–C6–C7–N2 = 28.1 (2)° and C3–C4–C13–N3 = 31.0 (2)°. The orientations of the two hydrazide moieties with respect to the benzene ring can be indicated by the dihedral angles between the mean planes of N1/N2/C8/C9 and N3/N4/C14/C15 and the benzene ring being 62.66 (7) and 63.84 (7)°, respectively. The torsion angles of N1–N2–C7–C6 = -165.58 (12)° and N4–N3–C13–C14 = -160.69 (12)° indicate that the two substituents are in (-)-anti-periplanar conformations. All bond lengths and angles are in normal values (Allen et al., 1987).

In the crystal packing in Fig. 2, the molecules are arranged in an anti-parallel manner and linked by N—H···O intermolecular hydrogen bonds and weak C—H···O intermolecular interactions (Table 1) into three dimensional networks. The crystal is further stabilized by a weak C—H···N intramolecular interaction.

Experimental

Initially isophthalic acid was converted to its methyl ester under refluxing condition with methanol and a catalytic amount of concentrated sulfuric acid. This ester was then refluxed with excess hydrazine hydrate and ethanol for three hours. After completion of the reaction, excess ethanol was evaporated out and the solid substance was washed well with water and dried under reduced pressure. The properly dried intermediate compound was treated with pivalic anhydride at 353 K for seven hours. The crude compound was extracted with chloroform after neutralizing the reaction mixture with aqueous sodium bicarbonate solution. The title compound was purified by column chromatography (Silica gel 100–200 mesh) using ethyl acetate as eluent to afford an off-white colored solid compound. Single crystals were grown by slow evaporation of CHCl₃/MeOH solution (v/v 1:1) (m.p. over 523 K).