N,N′-Bis(4-bi­phenyl­yl)­urea

George, S.; Nangia, A.

doi:10.1107/S1600536803010948

N,N′-Bis(4-biphenylyl)urea

S. George and A. Nangia

The crystal structure of the title compound, C₂₅H₂₀N₂O, has the N—H

O α-network typical of diaryl ureas.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803010948/fl6037sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536803010948/fl6037Isup2.hkl Contains datablock I

CCDC reference: 214864

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.005 Å
R factor = 0.043
wR factor = 0.133
Data-to-parameter ratio = 17.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.42
         From the CIF: _reflns_number_total               4296
         Count of symmetry unique reflns         2215
         Completeness (_total/calc)            193.95%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      2081
         Fraction of Friedel pairs measured     0.940
         Are heavy atom types Z>Si present           no
          ALERT: MoKa measured Friedel data cannot be used to
                 determine absolute structure in a light-atom
                 study EXCEPT under VERY special conditions.
                 It is preferred that Friedel data is merged in such cases.

Comment top

The title compound, (I) (Fig. 1), was synthesized as part of our ongoing study on the crystal packing in urea structures (George et al., 2001; George & Nangia, 2001). Symmetrical disubstituted ureas generally form a polar hydrogen-bond chain with anti NH donors and carbonyl O-atom acceptors in a bifurcated motif. Compound (I) crystallizes in the polar space group Pna2₁. Phenyl rings A and C, as well as B and D (see Fig. 1 for labelling), are twisted with respect to each other by −25.9 (5) and 24.2 (5)°, respectively (Table 1). Phenyl rings A and B are tilted with respect to the urea plane by 57.1 (5) and −37.1 (5)° (Table 1). The α-network is formed by a-glide-related molecules through N—H···O hydrogen bonds (Table 2 and Fig. 2). The outer phenyl rings (C and D) of c-translated molecules are close packed with no specific interactions. Screw-axis-related layers, viewed down the b axis, are arranged with a slight offset of hydrogen-bonded chains. Compound (I) crystallizes in the same space group as N,N'-diphenylurea [Dannecker et al., 1979; a = 9.091 (8), b = 10.535 (9) and c = 11.768 (10) Å], with similar a and b axes, but a longer c axis because of the biphenyl group.

Experimental top

Compound (I) was prepared by condensation of aryl amine with triphosgene (Corbin et al., 2001). A solution of triphosgene (300 mg, 1 mmol) in dichloromethane (3 ml) was added dropwise over 1 h to a solution of 4-biphenylamine (857 mg, 5 mmol) and 4-dimethylaminopyridine (773 mg, 6 mmol) in dichloromethane (7 ml). The resulting solution was stirred for 27 h or until no starting material remained (thin-layer chromatography). Nitrogen was bubbled through the reaction mixture to displace any unreacted phosgene and the solvent was removed under vacuum. The compound was recrystallized from dimethyl sulfoxide (m.p. above 538 K)

Computing details top

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: Xtal3.5 (Hall et al., 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLUTON-(C) (Spek, 1997); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. ORTEPII (Johnson, 1976) diagram and the atom-numbering scheme for (I); displacement ellipsoids are drawn at the 50% probablity level for non-H atoms.
	Fig. 2. Packing diagram of (I), showing the N—H···O hydrogen bonded α-network along the a axis.

N,N'-Bis(4-biphenylyl)urea top

Crystal data top

C₂₅H₂₀N₂O	D_x = 1.284 Mg m⁻³
M_r = 364.43	Melting point: above 538K K
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
a = 8.9673 (18) Å	Cell parameters from 25 reflections
b = 10.528 (2) Å	θ = 9.6–10.7°
c = 19.971 (4) Å	µ = 0.08 mm⁻¹
V = 1885.5 (7) Å³	T = 293 K
Z = 4	Plate, brown
F(000) = 768	0.15 × 0.14 × 0.10 mm

Data collection top

Enraf-Nonius CAD-4 diffractometer	R_int = 0.000
Radiation source: fine-focus sealed tube	θ_max = 27.4°, θ_min = 2.0°
Graphite monochromator	h = 0→11
ω scans	k = 0→13
4948 measured reflections	l = −25→25
4296 independent reflections	3 standard reflections every 90 min
2077 reflections with I > 2σ(I)	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H-atom parameters constrained
S = 0.84	w = 1/[σ²(F_o²)] where P = (F_o² + 2F_c²)/3
4296 reflections	(Δ/σ)_max < 0.001
253 parameters	Δρ_max = 0.11 e Å⁻³
1 restraint	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₂₅H₂₀N₂O	V = 1885.5 (7) Å³
M_r = 364.43	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 8.9673 (18) Å	µ = 0.08 mm⁻¹
b = 10.528 (2) Å	T = 293 K
c = 19.971 (4) Å	0.15 × 0.14 × 0.10 mm

Data collection top

Enraf-Nonius CAD-4 diffractometer	R_int = 0.000
4948 measured reflections	3 standard reflections every 90 min
4296 independent reflections	intensity decay: none
2077 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.043	1 restraint
wR(F²) = 0.133	H-atom parameters constrained
S = 0.84	Δρ_max = 0.11 e Å⁻³
4296 reflections	Δρ_min = −0.13 e Å⁻³
253 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N2	0.1638 (3)	0.7157 (3)	0.11870 (13)	0.0594 (7)
H2A	0.2548	0.6930	0.1125	0.071*
O1	−0.0375 (2)	0.8052 (2)	0.06709 (11)	0.0658 (6)
N1	0.1829 (3)	0.7899 (3)	0.01161 (13)	0.0626 (8)
H1A	0.2776	0.7811	0.0164	0.075*
C25	−0.0433 (4)	0.8899 (3)	−0.25062 (17)	0.0552 (8)
C24	0.0046 (3)	0.7715 (3)	0.21345 (15)	0.0536 (7)
H24A	−0.0281	0.8438	0.1912	0.064*
C23	−0.0453 (4)	0.6194 (3)	0.38394 (16)	0.0576 (8)
C22	0.0944 (3)	0.7733 (3)	0.06620 (17)	0.0542 (8)
C21	0.1275 (3)	0.8209 (3)	−0.05270 (16)	0.0555 (8)
C20	−0.1763 (4)	0.9549 (3)	−0.26107 (19)	0.0640 (9)
H20A	−0.2255	0.9900	−0.2245	0.077*
C19	0.0204 (3)	0.8698 (3)	−0.18220 (16)	0.0531 (8)
C18	0.1023 (3)	0.6893 (3)	0.18214 (15)	0.0512 (8)
C17	−0.0447 (3)	0.7467 (3)	0.27762 (14)	0.0533 (7)
H17A	−0.1116	0.8027	0.2975	0.064*
C16	0.1469 (3)	0.5811 (3)	0.21562 (16)	0.0603 (8)
H16A	0.2104	0.5237	0.1946	0.072*
C15	0.1615 (4)	0.7411 (4)	−0.10502 (16)	0.0747 (10)
H15A	0.2210	0.6702	−0.0976	0.090*
C14	0.0263 (4)	0.8397 (4)	−0.30704 (16)	0.0702 (10)
H14A	0.1159	0.7962	−0.3023	0.084*
C13	0.0980 (3)	0.5570 (3)	0.28036 (17)	0.0613 (8)
H13A	0.1295	0.4836	0.3020	0.074*
C12	−0.0096 (4)	0.9506 (3)	−0.12886 (17)	0.0611 (9)
H12A	−0.0661	1.0233	−0.1364	0.073*
C11	0.0024 (3)	0.6407 (3)	0.31365 (15)	0.0520 (8)
C10	−0.1767 (4)	0.6734 (3)	0.40791 (17)	0.0679 (9)
H10A	−0.2348	0.7223	0.3792	0.082*
C9	−0.0095 (5)	0.5295 (4)	0.4938 (2)	0.0871 (13)
H9A	0.0483	0.4811	0.5229	0.105*
C8	0.0426 (4)	0.9260 (3)	−0.06463 (17)	0.0638 (9)
H8A	0.0196	0.9813	−0.0298	0.077*
C7	0.0368 (4)	0.5469 (3)	0.42836 (18)	0.0735 (10)
H7A	0.1249	0.5091	0.4140	0.088*
C6	0.1078 (4)	0.7656 (4)	−0.16879 (16)	0.0728 (10)
H6A	0.1316	0.7101	−0.2034	0.087*
C5	−0.2225 (5)	0.6561 (4)	0.4730 (2)	0.0832 (12)
H5A	−0.3100	0.6941	0.4879	0.100*
C4	−0.1671 (5)	0.9162 (4)	−0.3788 (2)	0.0838 (12)
H4A	−0.2088	0.9235	−0.4213	0.101*
C3	−0.2376 (4)	0.9689 (4)	−0.3241 (2)	0.0756 (10)
H3A	−0.3261	1.0137	−0.3297	0.091*
C2	−0.0355 (5)	0.8532 (4)	−0.36990 (19)	0.0865 (12)
H2B	0.0133	0.8188	−0.4068	0.104*
C1	−0.1397 (6)	0.5829 (4)	0.5162 (2)	0.0905 (13)
H1B	−0.1716	0.5699	0.5600	0.109*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0338 (12)	0.082 (2)	0.0626 (16)	0.0031 (13)	0.0022 (12)	0.0007 (15)
O1	0.0316 (9)	0.1022 (17)	0.0634 (13)	0.0028 (11)	0.0016 (10)	−0.0046 (13)
N1	0.0337 (12)	0.099 (2)	0.0552 (15)	−0.0014 (14)	0.0029 (12)	0.0039 (15)
C25	0.0509 (16)	0.0493 (18)	0.065 (2)	−0.0028 (15)	0.0097 (16)	0.0080 (15)
C24	0.0457 (16)	0.0582 (18)	0.0569 (17)	−0.0026 (15)	−0.0019 (14)	−0.0018 (15)
C23	0.0517 (18)	0.061 (2)	0.060 (2)	−0.0127 (17)	−0.0065 (16)	0.0042 (16)
C22	0.0385 (14)	0.068 (2)	0.0563 (17)	−0.0059 (15)	−0.0003 (16)	−0.0046 (17)
C21	0.0360 (15)	0.068 (2)	0.063 (2)	−0.0012 (15)	0.0091 (15)	0.0036 (17)
C20	0.057 (2)	0.060 (2)	0.075 (2)	−0.0007 (17)	0.0068 (18)	0.0087 (18)
C19	0.0449 (16)	0.0516 (18)	0.063 (2)	−0.0008 (15)	0.0126 (16)	0.0068 (15)
C18	0.0325 (13)	0.063 (2)	0.0584 (19)	−0.0059 (15)	−0.0020 (14)	−0.0023 (16)
C17	0.0470 (16)	0.0555 (18)	0.0575 (18)	0.0004 (15)	0.0003 (15)	−0.0049 (17)
C16	0.0427 (16)	0.067 (2)	0.071 (2)	0.0084 (16)	0.0073 (16)	−0.0053 (18)
C15	0.072 (2)	0.082 (3)	0.070 (2)	0.032 (2)	0.0076 (19)	0.006 (2)
C14	0.068 (2)	0.079 (2)	0.064 (2)	0.0095 (19)	0.0104 (19)	0.0016 (18)
C13	0.0513 (17)	0.058 (2)	0.074 (2)	0.0033 (16)	−0.0035 (18)	0.0080 (18)
C12	0.058 (2)	0.0539 (19)	0.071 (2)	0.0066 (17)	0.0106 (17)	0.0007 (16)
C11	0.0368 (14)	0.0589 (19)	0.0603 (19)	−0.0096 (14)	−0.0034 (13)	−0.0046 (15)
C10	0.063 (2)	0.076 (2)	0.066 (2)	0.0021 (19)	0.0026 (18)	0.0079 (19)
C9	0.100 (3)	0.089 (3)	0.072 (3)	−0.010 (3)	−0.020 (2)	0.022 (2)
C8	0.0577 (19)	0.063 (2)	0.071 (2)	0.0020 (17)	0.0079 (18)	−0.0079 (18)
C7	0.067 (2)	0.084 (3)	0.070 (2)	0.000 (2)	−0.008 (2)	0.013 (2)
C6	0.080 (2)	0.077 (2)	0.061 (2)	0.027 (2)	0.0107 (19)	−0.008 (2)
C5	0.093 (3)	0.086 (3)	0.070 (2)	0.003 (2)	0.016 (2)	0.009 (2)
C4	0.082 (3)	0.094 (3)	0.075 (3)	−0.007 (2)	−0.006 (2)	0.007 (2)
C3	0.059 (2)	0.076 (3)	0.092 (3)	−0.006 (2)	−0.006 (2)	0.016 (2)
C2	0.095 (3)	0.102 (3)	0.062 (2)	0.003 (3)	0.011 (2)	0.000 (2)
C1	0.112 (3)	0.092 (3)	0.068 (3)	−0.014 (3)	0.009 (3)	0.010 (2)

Geometric parameters (Å, º) top

N2—C22	1.362 (4)	C19—C6	1.375 (4)
N2—C18	1.409 (4)	C19—C12	1.390 (4)
O1—C22	1.230 (3)	C18—C16	1.381 (4)
N1—C22	1.360 (4)	C17—C11	1.394 (4)
N1—C21	1.415 (4)	C16—C13	1.389 (4)
C25—C20	1.391 (4)	C15—C6	1.386 (4)
C25—C14	1.392 (4)	C14—C2	1.380 (5)
C25—C19	1.496 (4)	C13—C11	1.398 (4)
C24—C17	1.380 (4)	C12—C8	1.390 (4)
C24—C18	1.381 (4)	C10—C5	1.376 (5)
C23—C7	1.382 (4)	C9—C1	1.372 (6)
C23—C10	1.392 (5)	C9—C7	1.384 (5)
C23—C11	1.485 (4)	C5—C1	1.373 (6)
C21—C8	1.365 (4)	C4—C2	1.366 (5)
C21—C15	1.375 (5)	C4—C3	1.378 (5)
C20—C3	1.382 (5)

C22—N2—C18	127.0 (2)	C16—C18—N2	119.0 (3)
C22—N1—C21	123.5 (3)	C24—C17—C11	122.2 (3)
C20—C25—C14	116.7 (3)	C18—C16—C13	120.7 (3)
C20—C25—C19	122.3 (3)	C21—C15—C6	120.5 (3)
C14—C25—C19	120.9 (3)	C2—C14—C25	121.2 (4)
C17—C24—C18	120.4 (3)	C16—C13—C11	121.4 (3)
C7—C23—C10	117.1 (3)	C8—C12—C19	121.9 (3)
C7—C23—C11	122.5 (3)	C17—C11—C13	116.4 (3)
C10—C23—C11	120.5 (3)	C17—C11—C23	121.5 (3)
O1—C22—N1	122.5 (3)	C13—C11—C23	122.1 (3)
O1—C22—N2	123.4 (3)	C5—C10—C23	121.6 (4)
N1—C22—N2	114.1 (2)	C1—C9—C7	120.6 (4)
C8—C21—C15	119.1 (3)	C21—C8—C12	120.0 (3)
C8—C21—N1	122.8 (3)	C23—C7—C9	121.3 (4)
C15—C21—N1	118.1 (3)	C19—C6—C15	121.7 (3)
C3—C20—C25	122.0 (4)	C1—C5—C10	120.4 (4)
C6—C19—C12	116.7 (3)	C2—C4—C3	119.2 (4)
C6—C19—C25	120.6 (3)	C4—C3—C20	119.8 (4)
C12—C19—C25	122.6 (3)	C4—C2—C14	121.0 (4)
C24—C18—C16	118.8 (3)	C9—C1—C5	119.1 (4)
C24—C18—N2	122.1 (3)

C12—C19—C25—C20	−25.9 (5)	C22—N1—C21—C8	57.1 (5)
C17—C11—C23—C10	24.2 (5)	C22—N2—C18—C24	−37.1 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	2.15	2.918 (3)	149
N2—H2A···O1ⁱ	0.86	2.07	2.878 (3)	156

Symmetry code: (i) x+1/2, −y+3/2, z.

Experimental details

Crystal data
Chemical formula	C₂₅H₂₀N₂O
M_r	364.43
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	293
a, b, c (Å)	8.9673 (18), 10.528 (2), 19.971 (4)
V (Å³)	1885.5 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.15 × 0.14 × 0.10

Data collection
Diffractometer	Enraf-Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4948, 4296, 2077
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.133, 0.84
No. of reflections	4296
No. of parameters	253
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.13

Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, Xtal3.5 (Hall et al., 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLUTON-(C) (Spek, 1997), SHELXL97.