2,2′-(Biphenyl-2,2′-diyldi­oxy)diaceto­hydrazide

Farooq Ibad; Asra Mustafa; Muhammad Raza Shah; Donald VanDerveer

doi:10.1107/S1600536808014864

. 2008 May 21;64(Pt 6):o1130–o1131. doi: 10.1107/S1600536808014864

2,2′-(Biphenyl-2,2′-diyldioxy)diacetohydrazide

Farooq Ibad ^a, Asra Mustafa ^a, Muhammad Raza Shah ^a,^*, Donald VanDerveer ^b

PMCID: PMC2961455 PMID: 21202641

Abstract

In the molecule of the title compound, C₁₆H₁₈N₄O₄, the dihedral angle between the mean planes of the two benzene rings is 56.76 (5)°. The crystal structure reveals extensive intermolecular hydrogen bonds between carbonyl O atoms and primary amines, as well as between primary and secondary amines of hydrazide, forming rings of R ₂ ²(10) and R ₂ ²(6) motifs, respectively. The structure is further stabilized by intramolecular and non-classical hydrogen bonds of the types N—H⋯O and C—H⋯O, respectively. The structure does not show any π–π interactions.

Related literature

For related literature see: Dekeyser et al. (2003 ▶); Ali et al. (2008 ▶); Baudry et al. (2006 ▶); Bhat et al. (1974 ▶); Etter (1990 ▶); Kakefuda et al. (2002 ▶); Litvinchuk et al. (2004 ▶); Priebe et al. (2008 ▶); Sisson et al. (2006 ▶); Thaker & Patel (2008 ▶); Yan et al. (1993 ▶).

Experimental

Crystal data

C₁₆H₁₈N₄O₄
M _r = 330.34
Triclinic,
a = 8.4041 (17) Å
b = 9.7148 (19) Å
c = 10.465 (2) Å
α = 99.27 (3)°
β = 92.50 (3)°
γ = 113.85 (3)°
V = 765.7 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 153 (2) K
0.31 × 0.29 × 0.22 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ▶) T _min = 0.968, T _max = 0.977
5673 measured reflections
2695 independent reflections
2440 reflections with I > 2σ(I)
R _int = 0.009

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.092
S = 1.05
2695 reflections
237 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2006 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808014864/pv2081sup1.cif

e-64-o1130-sup1.cif^{(19.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808014864/pv2081Isup2.hkl

e-64-o1130-Isup2.hkl^{(132.3KB, 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—H1A⋯O4ⁱ	0.924 (14)	2.192 (15)	3.059 (2)	155.7 (15)
N1—H1B⋯O4ⁱⁱ	0.930 (14)	2.510 (17)	3.0112 (18)	114.1 (13)
N3—H3⋯N4ⁱⁱⁱ	0.900 (13)	2.191 (15)	2.9524 (18)	141.9 (14)
N4—H4B⋯O1^iv	0.936 (14)	2.267 (16)	2.9873 (18)	133.3 (14)
N1—H1B⋯O1	0.930 (14)	2.348 (17)	2.7873 (18)	108.6 (13)
N2—H2⋯O2	0.906 (14)	2.118 (17)	2.5375 (16)	107.1 (13)
N3—H3⋯O3	0.900 (13)	2.230 (16)	2.5977 (17)	103.9 (12)
C5—H5A⋯N1^v	0.95	2.53	3.359 (2)	146
C11—H11A⋯O1^vi	0.95	2.47	3.292 (2)	145

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

Acknowledgments

The authors thank the Higher Education Commission of Pakistan for financial support.

supplementary crystallographic information

Comment

Biphenyl hydrazides are of crucial importance in the design and synthesis of novel advanced functional materials (Thaker & Patel, 2008) and compounds of biological importance (Kakefuda et al., 2002; Dekeyser et al., 2003). Our interest in the synthesis of biphenyl dihydrazide arose from the fact that we wanted to attach macrocycles like porphyrin to diphenyl dicarboxylic acid and carboxylic substituted oligo(p-phenylene)s (Litvinchuk et al., 2004) to form functionalized pores (Sisson et al., 2006; Baudry et al., 2006). The coupling of amino-substituted macrocycles gave poor yields so we changed the strategy and synthesized carboxylic substituted macrocycles and hydrazide substituted biphenyls. Studies on the coupling of these biphenyl hydrazides and macrocycles are in progress. In this paper, we report the synthesis and crystal structure of the title compound, (I).

The molecules of the title compound (Fig. 1) are held together by intermolecular hydrogen bonds involving carbonyl O-atoms and primary amines as well as primary amines and secondary amines of the type N—H···O and N—H···H, respectively, which stabilize the crystal structure (Fig. 2) resulting in ten and six membered which may be described in the graph set notation as R₂²(10) and R₂²(6) (Etter, 1990). There are three intramolecular hydrogen bonds in addition to non-classical hydrogen bonds involving phenyl H-atoms and a carbonyl oxygen and a primary amine; details of hydrogen bonding geometry have been provided in Table 1.

The C1—O1 and C16—O4 distances in (I) are 1.2284 (17)Å and 1.2338 (16) Å, respectively, typical of double bonds (Yan et al., 1993), whereas the distances C1—N2 and C16—N3 at 1.3320 (18)Å and 1.3291 (18)Å are consistent with those reported (Priebe et al., 2008), suggesting partial double bond character. Similarly, the distances N1—N2 and N3—N4, 1.4198 (17)Å and 1.4196 (17) Å, respectively, are typical for a single bond, which are in agreement with those of the analogous compound (Bhat et al., 1974), suggesting that the title compound exists as resonance hybrid between a polar and a neutral form.

Experimental

Diethyl 2,2'-(biphenyl-2,2'-diylbis(oxy))diacetate (500 mg, 1.4 mmol) was refluxed in the presence of hydrazine hydrate (5 ml, 103 mmol) in ethanol (10 ml) at 353 K for 2 h, the reaction mixture was cooled down to room temperature and then poured into 10 ml of water. The reaction mixture was extracted three times with ethyl acetate. The combined organic phases were concentrated under reduced pressure. The crude residue was dissolved in ethanol and slow evaporation of ethanol afforded colorless crystals (276 mg, 60% yield) suitable for XRD analysis.