3-Diethyl­carbamoyl-2′,4′-difluoro­biphenyl-4-yl 2,6-dichloro-5-fluoro­pyridine-3-carboxyl­ate

Chun-nian Xia; Yu Zhou; You-bao Chen; Guang-xiang Zhong

doi:10.1107/S1600536812025354

. 2012 Jun 13;68(Pt 7):o2047. doi: 10.1107/S1600536812025354

3-Diethylcarbamoyl-2′,4′-difluorobiphenyl-4-yl 2,6-dichloro-5-fluoropyridine-3-carboxylate

Chun-nian Xia ^a,^*, Yu Zhou ^a, You-bao Chen ^a, Guang-xiang Zhong ^a

PMCID: PMC3393315 PMID: 22807872

Abstract

In the title compound, C₂₃H₁₇Cl₂F₃N₂O₃, the molecular conformation is significantly strained: atoms O, C(=O) and C attached to the central benzene ring deviate from its plane by 0.118 (2), 0.139 (2) and 0.174 (2) Å, respectively. In the crystal, weak C—H⋯O interactions link the molecules into chains along [110]. The crystal packing exhibits short intermolecular Cl⋯F [2.9840 (16) Å] and Cl⋯Cl [3.2957 (12) Å] contacts.

Related literature

For details of the synthesis, see: Zhong et al. (2009 ▶, 2010 ▶).

Experimental

Crystal data

C₂₃H₁₇Cl₂F₃N₂O₃
M _r = 497.29
Triclinic,
a = 10.635 (3) Å
b = 10.888 (3) Å
c = 11.310 (3) Å
α = 96.838 (1)°
β = 109.213 (1)°
γ = 116.017 (3)°
V = 1056.5 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 153 K
0.47 × 0.45 × 0.41 mm

Data collection

Rigaku AFC10/Saturn724+ diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.848, T _max = 0.866
10358 measured reflections
4752 independent reflections
3984 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.082
S = 1.00
4752 reflections
300 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2008 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812025354/cv5305sup1.cif

e-68-o2047-sup1.cif^{(22.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812025354/cv5305Isup2.hkl

e-68-o2047-Isup2.hkl^{(228KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812025354/cv5305Isup3.cml

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
C2—H2⋯O3ⁱ	0.95	2.35	3.287 (2)	170

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Symmetry code: (i) Inline graphic .

Acknowledgments

This project was supported by the Educational Commission of Zhejiang Province (grant No. GD09071160185). The authors acknowledge Professor Kai-Bei Yu at the State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, for the data collection.

supplementary crystallographic information

Comment

Fluorine-containing drugs, such as tegadifur, flutamide, ciprofloxacin - non-steroid anti-inflammatory drugs, have been studied due to their special properties (Zhong et al., 2009, 2010). As a continuation of their study, we present here the title compound (I) (Fig. 1).

The molecular conformation of (I) is significantly strained - atoms O1, C19 and C6 attached to the central benzene ring C7—C12 deviate from its plane at 0.118 (2), 0.139 (2) and 0.174 (2) Å, respectively. The atoms of C1–C6, F1 and F2 are almost coplanar, deviating from the mean plane within 0.0249 (12) A °. The atoms C13–C18, N1, F3 and Cl1 are coplanar, deviating from the mean plane within 0.0442 (10) A °, and the deviation of Cl1, O2 from the plane is 0.1047 (15) A °, 0.5851 (17) A °, respectively. The diethylamine group shows a normal twist conformation. The mean planes of C1—C6/F1/F2 and C13—C18/N1/F3/Cl1 form the dihedral angles of 34.62 (5) and 87.45 (4)°, respectively, with the central benzene ring. The adjacent substituent (C10 and C11 of the parent ring) remove away or reverse each other, which owes to the Cl and F atoms showing greater repulsive force. This phenomenon is samilar to that observed in 20,40-difluoro-4-[(4-chlorobenzoyl)oxy]-N-[4-nitro-3- (trifluoromethyl)phenyl]-[1,10-biphenyl]-3-carboxamide (Zhong et al., 2010).

In the crystal, weak C—H···O interactions (Table 1) link the molecules related by translation in [110] into chains. The crystal packing exhibits short intermolecular Cl···F [2.9840 (16) Å] and Cl···Cl [3.2957 (12) Å] contacts.

Experimental

The title compound was synthesized according to the known methods (Zhong et al., 2009, 2010). M.p. 125-127°C. ¹HNMR (500 MHz, CDCl₃, δ ppm): 1.13 (t, 3H, J =7.0 Hz, -CH₃), 1.15 (t, 3H, J =7.0 Hz, -CH₃), 3.31 (q, 2H, J=7.0 Hz, -CH₂), 3.50 (q, 2H, J=7.0 Hz, -CH₂), 6.95 (t, 1H, J=8.5 Hz), 7.00 (t, 1H, J=8.5 Hz), 7.41(d, 1H, J=8.5 Hz), 7.42 (q, 1H, J=8.5 Hz), 7.50 (s, 1H), 7.60 (d, 1H, J=8.5 Hz), 8.24 (d, 1H, J=7.0 Hz). MS: m/z 496 (M⁺, 11.85), 425 (6.50), 233 (22.78),232 (7.63), 195 (6.76), 191 (62.99), 164 (4.63), 72 (23.72). The solid product was dissolved in butanone-ethanol (4:1 v/v) and the solution evaporated gradually at room temperature to afford colorless single crystals of (I).