A new polymorph of 1,3-bis­(penta­fluoro­phen­yl)urea

Tsunehisa Okuno

doi:10.1107/S1600536813007836

. 2013 Mar 28;69(Pt 4):o608. doi: 10.1107/S1600536813007836

A new polymorph of 1,3-bis(pentafluorophenyl)urea

Tsunehisa Okuno ^a,^*

PMCID: PMC3629646 PMID: 23634133

Abstract

The title compound, C₁₃H₂F₁₀N₂O, has been previously described in the space group Pbca with Z = 8 [Jai-nhuknan et al. (1997 ▶). Acta Cryst. C53, 455–457]. The current P2₁2₁2₁ polymorph was obtained from a tetrahydrofuran solution. The pentafluorophenyl rings make dihedral angles of 50.35 (6) and 54.94 (6)° with the urea fragment, in close accord with those reported for the first polymorph. In the crystal, both of the N—H groups donate H atoms to the same carbonyl O atom, forming a one-dimensional molecular array along the a axis. There are close contacts between perfluorophenyl C atoms within the array [3.228 (3) Å] and halogen bonds are also observed between the arrays [F⋯F = 2.709 (2) and 2.7323 (18) Å].

Related literature

For the structure of the first reported ploymorph, see: Jai-nhuknan et al. (1997 ▶). For the related structure of 1,3-diphenylurea, see: Dannecker et al. (1979 ▶). For background to organofluorine chemistry, see: Chambers (2004 ▶). graphic file with name e-69-0o608-scheme1.jpg

Experimental

Crystal data

C₁₃H₂F₁₀N₂O
M _r = 392.16
Orthorhombic,
a = 4.5798 (7) Å
b = 9.5411 (16) Å
c = 29.136 (5) Å
V = 1273.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 93 K
0.15 × 0.15 × 0.03 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: numerical (NUMABS; Rigaku, 1999 ▶) T _min = 0.978, T _max = 0.993
10307 measured reflections
1993 independent reflections
1941 reflections with F ² > 2σ(F ²)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.080
S = 1.09
1991 reflections
241 parameters
2 restraints
Only H-atom coordinates refined
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: CrystalClear (Rigaku, 2008 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR92 (Altomare, et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: CrystalStructure (Rigaku, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(23.7KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813007836/ff2101sup1.cif

e-69-0o608-sup1.cif^{(23.7KB, cif)}

Click here for additional data file.^{(98KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813007836/ff2101Isup2.hkl

e-69-0o608-Isup2.hkl^{(98KB, hkl)}

Click here for additional data file.^{(5.4KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813007836/ff2101Isup3.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
N1—H1⋯O1ⁱ	0.864 (18)	2.057 (18)	2.850 (3)	152 (3)
N2—H2⋯O1ⁱ	0.879 (18)	2.008 (18)	2.825 (3)	154 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by ‘Research for Promoting Technological Seeds’ of the Japan Science and Technology Agency (JST).

supplementary crystallographic information

Comment

Perfluoro aromatic compounds have attracted interest from the viewpoint of the electronic and structural comparison with the original compounds (Chambers, 2004). The title compound, (I), is a perfluoro compound of 1,3-diphenylurea (Dannecker et al., 1979). Previously, (I) was isolated in an orthorhombic Pbca polymorph with Z = 8 [Jai-nhuknan et al., 1997]. A new orthorhombic P2₁2₁2₁ polymorph was obtained by recrystallization from a tetrahydrofuran solution.

The dihedral angle between the C1—C6/F1—F5 (r.m.s. deviation = 0.0223 Å) and the C7—C12/F6—F10 (r.m.s. deviation = 0.0181 Å) pentafluorophenyl rings is 30.93 (3)°, which is smaller than that of the reported polymorph. The pentafluorophenyl rings make dihedral angles of 50.35 (6)° and 54.94 (6)°, respectively, with the C13/N1/N2/O1 urea fragment (r.m.s. deviation = 0.0011 Å), and this situation is almost accordance with the reported polymorph.

Both of the N—H groups in one molecule donate protons to the same carbonyl O atom, forming a one-dimensional molecular array along the a axis, where the N···O distances were 2.850 (3) Å for N1···O1ⁱ and 2.825 (3) Å for N2···O1ⁱ [Symmetry code: (i) x + 1, y, z] (Figure 2). There are close contacts between perfluorophenyl carbons within the array, where the C2···C5ⁱ distance is 3.228 (3) Å. Halogen-bonds are also recognized between the arrays. The distances of F2···F10ⁱⁱ and F1···F5ⁱⁱⁱ are 2.709 (2) Å and 2.7323 (18) Å, respectively [Symmetry codes: (ii) -x + 1, y + 1/2, -z + 1/2 (iii)-x + 2, y + 1/2, -z + 1/2.] (Figure 2).

Experimental

The title compound was commercially purchased and recrystallized from a tetrahydrofuran solution.