(Z)-N-(2,6-Diiso­propyl­phen­yl)-4-nitro­benzimidoyl chloride

Gamal A El-Hiti; Keith Smith; Dyfyr Heulyn Jones; Ali Masmali; Benson M Kariuki

doi:10.1107/S1600536813020862

. 2013 Aug 7;69(Pt 9):o1384. doi: 10.1107/S1600536813020862

(Z)-N-(2,6-Diisopropylphenyl)-4-nitrobenzimidoyl chloride

Gamal A El-Hiti ^a,^*, Keith Smith ^b, Dyfyr Heulyn Jones ^b, Ali Masmali ^a, Benson M Kariuki ^b,^*

PMCID: PMC3884373 PMID: 24427026

Abstract

In the title compound, C₁₉H₂₁ClN₂O₂, the aromatic rings are approximately perpendicular to each other, subtending a dihedral angle of 87.7 (1)°. In the crystal, the 4-nitrophenyl groups of pairs of neighbouring molecules are parallel and oriented head-to-tail with a ring centroid–centroid distance of 3.9247 (12) Å, leading to a π–π interaction between the pair. The faces of each phenyl ring of the 2,6-diisopropylphenyl group interact with two different groups, viz. a chloro group of an adjacent molecule on one side and the edge of the 4-nitrophenyl ring of a second molecule on the other side.

Related literature

For the synthesis and applications of imidoyl chlorides, see: Pelter et al. (1975 ▶); Manley & Bilodeau (2002 ▶); Cunico & Pandey (2005 ▶); Raussukana et al. (2006 ▶); Zheng & Alper (2008 ▶); Kuszpit et al. (2011 ▶). For a related structure of an imidoyl chloride, see: Seidelmann et al. (1998 ▶).

Experimental

Crystal data

C₁₉H₂₁ClN₂O₂
M _r = 344.83
Triclinic,
a = 8.2988 (4) Å
b = 10.4667 (3) Å
c = 10.9665 (3) Å
α = 75.568 (2)°
β = 85.411 (2)°
γ = 74.145 (2)°
V = 887.33 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 150 K
0.35 × 0.20 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.924, T _max = 0.967
6021 measured reflections
4232 independent reflections
3108 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.062
wR(F ²) = 0.173
S = 1.06
4232 reflections
222 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP99 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813020862/is5293sup1.cif

e-69-o1384-sup1.cif^{(24.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813020862/is5293Isup2.hkl

e-69-o1384-Isup2.hkl^{(203.1KB, hkl)}

Click here for additional data file.^{(6.2KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813020862/is5293Isup3.cml

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

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

Cg1 and Cg2 are the centroids of the C1–C6 and C8–C13 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯Cg2ⁱ	0.95	2.67	3.511 (2)	147
C16—H16B⋯Cg1ⁱⁱ	0.98	2.79	3.663 (3)	149

Open in a new tab

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

Acknowledgments

The authors would like to extend their appreciation to the Deanship of Scientific Research at King Saud University for its funding for this research through the research group project RGP-VPP-239.

supplementary crystallographic information

1. Comment

The title compound I, a useful synthetic intermediate, was synthesized in good yield by the reaction of N-(2,6-diisopropylphenyl)-4-nitrobenzamide with phosphorus pentachloride. Imidoyl chlorides are useful reactive intermediates in syntheses of ketones from trialkylcyanoborates (Pelter et al., 1975), of highly substituted 2-imidazolines via a ring-expansion reaction with aziridines (Kuszpit et al., 2011), and by in situ reaction with pyridine-1-oxides to give 2-aminopyridine amides (Manley et al., 2002). They have also been used as precursors to α-iminoamides (Cunico et al., 2005), isoquinolin-1(2H)-ones via a palladium-catalyzed reaction with diethyl(2-iodoaryl)malonates (Zheng et al., 2008), and 1,3-oxathiolanones and benzoxathianones by reaction with mercaptocarboxylic acids (Raussukana et al., 2006). The X-ray crystal structure of N-(diethylaminothiocarbonyl)ferrocenecarbimidoyl chloride has been reported (Seidelmann et al., 1998).

In the molecule (Fig. 1), the aromatic rings of the 2,6-diisopropylphenyl and 4-nitrophenyl groups are approximately perpendicular to each other; the dihedral angle between the least-squares planes through the rings is 87.7 (1)°. The molecule has no strong hydrogen bond donor and the crystal structure is shown in Figure 2. The 4-nitrophenyl groups of neighboring molecules are parallel and oriented head-to-tail with a ring centroid-centroid distance of 3.9247 (12) Å, leading to a π–π interaction (Fig. 3). One face of the phenyl ring of the 2,6-diisopropylphenyl group interacts with the chloro group of an adjacent molecule (C7—Cl1···Cg2) and the other face of the same ring interacts with the edge of the 4-nitrophenyl ring of a second molecule (C6—H6···Cg2; Fig. 4); Cg2 is the centroid of the C8–C13 ring. Another interaction, C16—H16B···Cg1, is also observed; Cg1 is the centroid of the C1–C6 ring.

2. Experimental

Synthesis ofN-(2,6-diisopropylphenyl)-4-nitrobenzimidoyl chloride (I)

An oven dried two necked 100 ml flask equipped with a magnetic stirrer, septum-capped reflux condenser and septum was flushed with N₂ and phosphorus pentachloride (4.42 g, 21 mmol) and dry toluene (40 ml) were added. The mixture was stirred for 5 min then N-(2,6-diisopropylphenyl)-4-nitrobenzamide (6.90 g, 21 mmol) was quickly added to the flask under a fast stream of N₂, and the septum replaced by a stopper. The mixture was heated to reflux for 2 h, whereupon it became homogeneous and gas evolution was observed. Phosphorus oxychloride and toluene were removed under reduced pressure and the crude product was quickly extracted with hot diethyl ether (3 × 80 ml). The diethyl ether washings were evaporated under a fast stream of N₂ overnight, during which process bright yellow prisms of N-(2,6-diisopropylphenyl)-4-nitrobenzimidoyl chloride (6.93 g, 95%) separated; m.p. 144–146 °C. HREI⁺–MS m/z: calcd for C₁₉H₂₁N₂O₂³⁵Cl 344.1292, found 344.1301.