2-(3-Chloro­benzo­yl)-3-(3,4-di­chloro­phen­yl)-1-(4-ferrocenylphen­yl)guanidine

Rukhsana Gul; Azim Khan; Amin Badshah; M Nawaz Tahir

doi:10.1107/S1600536813021892

. 2013 Aug 10;69(Pt 9):m486. doi: 10.1107/S1600536813021892

2-(3-Chlorobenzoyl)-3-(3,4-dichlorophenyl)-1-(4-ferrocenylphenyl)guanidine

Rukhsana Gul ^a, Azim Khan ^a, Amin Badshah ^b, M Nawaz Tahir ^c,^*

PMCID: PMC3884485 PMID: 24426986

Abstract

In the title compound, [Fe(C₅H₅)(C₂₅H₁₇Cl₃N₃O)], the isolated cyclopentadienyl (Cp) ring is disordered over two set of sites in a 0.577 (8):0.423 (8) ratio. The dihedral angle between the other Cp ring and its attached benzene ring is 13.6 (3)°, and that between the benzene ring and the guanidine group is 64.8 (2)°. One of the N—H groups forms both an intra- and an intermolecular N—H⋯O hydrogen bond; the other N—H group does not form any hydrogen bonds. In the crystal, pairs of the intermolecular N—H⋯O hydrogen bonds link the molecules into inversion dimers.

Related literature

For a related structure, see: Bequeath et al. (2007 ▶). For further synthetic details, see: Gul et al. (2013 ▶).

Experimental

Crystal data

[Fe(C₅H₅)(C₂₅H₁₇Cl₃N₃O)]
M _r = 602.71
Monoclinic,
a = 17.674 (3) Å
b = 6.1352 (12) Å
c = 23.961 (5) Å
β = 95.359 (9)°
V = 2586.8 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.92 mm⁻¹
T = 296 K
0.32 × 0.15 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009) ▶ T _min = 0.757, T _max = 0.882
20020 measured reflections
4828 independent reflections
2612 reflections with I > 2σ(I)
R _int = 0.088

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.122
S = 1.01
4828 reflections
319 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: APEX2 (Bruker, 2009) ▶; cell refinement: SAINT (Bruker, 2009) ▶; data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813021892/hb7118sup1.cif

e-69-0m486-sup1.cif^{(46KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813021892/hb7118Isup2.hkl

e-69-0m486-Isup2.hkl^{(264.8KB, 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—H1⋯O1	0.86	1.97	2.616 (4)	131
N1—H1⋯O1ⁱ	0.86	2.55	3.193 (5)	132

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan.

supplementary crystallographic information

1. Comment

The crystal structure of p-ferrocenylaniline (Bequeath et al., 2007) has been published. As part of our studies in this area, the title compound (I, Fig. 1) has been prepared.

In (I), the benzene ring A (C11—C16), dichlorophenyl B (C18—C23/CL1/CL2) and 3-chlorobenzoyl C (O1/C24—C30/CL3) are essentailly planar with r.m.s. deviation of 0.0075, 0.0154 and 0.0512 Å, respectively. The guanidine group D (C17/N1/N2/N3) is also close to planar with r.m.s. deviation of 0.0107 Å from the mean square plane. The dihedral angle between A/B, A/C, A/D, B/C, B/D and C/D is 59.1 (9)°, 52.0 (9)°, 64.8 (2)°, 10.2 (1)°, 16.6 (2)° and 14.8 (2)°, respectively. In the crystal, the molecules are dimerized due to intra and intermolecular H-bondings of N—H···O type (Table 1, Fig. 2).

2. Experimental

The synthesis of the compound (I) was achieved in four steps. In the first step; 4- nitrophenylferrocene was made by the coupling of ferrocene with diazonium salts of nitroaniline using phase transfer catalyst (Gul et al., 2013). In the second step; this nitro phenyl ferrocene was reduced into 4-ferrocenylaniline using palladium on charcoal and hydrazine as reducing agent. In the third step, 3-chlorobenzoyl-3,4-dichlorophenyl thiourea was synthesized by the coupling of substituted aniline with thiocynates in acetone. In the fourth step; the thiourea was mixed with the 4-ferrocenyl aniline in dimethylformamide (DMF) in equimolar ratio with two equivalents of triethylamine (Et₃N). The temperature was maintained below 278 K using an ice bath and one equivalent of mercuric chloride (HgCl₂) was added to the reaction mixture with vigorous stirring. The ice bath was removed after 30 minutes while the stirring continued overnight. The progress of the reaction was monitored by thin layer chromatography (TLC) till the completion of reaction. Chloroform (CHCl₃, 20 ml) was added to the reaction mixture and the suspension was filtered through a sintered glass funnel to remove the mercuric sulfide (HgS) residue. The solvents from filtrate were evaporated under reduced pressure and residue was re-dissolved in dichloromethane (CH₂Cl₂, 20 ml), washed with water (4 × 30 ml) and dried the organic phase over anhydrous magnesium sulfate (MgSO₄). The solvent was evaporated and residue was purified by column chromatography to afford orange needles.