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In the crystal structure of the title compound, C13H12N2O, N—H(anti)...O hydrogen bonds produce the so-called urea α-network and the N—H(syn) donor forms an unconventional N—H...π hydrogen bond.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101005807/jz1458sup1.cif
Contains datablocks m2, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101005807/jz1458Isup2.hkl
Contains datablock I

CCDC reference: 167007

Comment top

The packing motifs of substituted ureas have been studied in the context of crystal engineering, supramolecular synthesis and polymorphism (Coe et al., 1997; Hollingsworth et al., 1994; Kane et al., 1995). Phenylurea (Kashino & Haisa, 1997; space group P21) contains the one-dimensional α-network, which in turn is linked to form two-dimensional β-sheet through N—H···O hydrogen bonds. Given that a biphenyl group tends to induce non-centrosymmetry in crystal packing (Sarma et al., 1997; Swift & Ward, 2000), we have now determined the crystal structure of 4-biphenylylurea, (I). Although the structure of (I) is centrosymmetric (Pbca) and hence of no utility for second harmonic generation, the existence of an unconventional N—H···π hydrogen bond (π refers to phenyl ring centroid) deserves discussion. Weak N—H···π type hydrogen bonding (Desiraju & Steiner, 1999) in small molecule (Malone et al., 1997) and protein (Steiner & Koellner, 2001) crystal structures has gained recent attention. \sch

The biphenyl moiety is twisted by an angle of 45.41 (17)° about the C—C bond (Fig. 1). Molecules of (I) are connected by N—H(anti)···O hydrogen bonds along [100]. The biphenyl groups interdigitate between α-networks, with the phenyl rings involved in edge-to-face herringbone packing. The syn N—H group forms an N—H···π interaction with the phenyl ring of a screw axis related molecule (Fig. 2). Malone et al. (1997) have classified N—H···π hydrogen bonds into six categories depending on the approach geometry of N—H vector to different regions of the phenyl ring. In this nomenclature, the N—H···π interaction in (I) is of type II: dπcH = 2.57 Å, α = 169.0°, angle of H···π vector with the plane of phenyl ring (θ) = 76.8°, offset distance of H atom from the centroid of phenyl ring (d) = 0.58 Å. Type II N—H···π geometry is present in about 10% of crystal structures (Malone et al., 1997).

A search of the Cambridge Structural Database (version 5.19, 24400 entries, October 2000 update, Allen & Kennard, 1993) for N—H···π contacts in mono-substituted urea structures in the range 1.8 < H···π < 3.0 Å and 120 < N—H···π < 180° furnished two hits (BODSAO: Pickering & Small, 1982; DISCAJ: Goldberg et al., 1985). The corresponding formulae are given in the Scheme. The crystal structure of the N,N-dimethylformamide solvate of triphenylmethyl urea (DISCAJ, space group Cc) has two N—H···π contacts (N24—H56···π: 2.69 Å, 166.4°; N1—H53···π: 2.63 Å, 171.8°). This study shows that correspondence between molecular and crystal structure (Desiraju, 1999) can be difficult to establish even for simple molecules with robust hydrogen bonding supramolecular synthons.

Experimental top

Compound (I) was prepared as described by Vogel (1991). 4-Aminobiphenyl (507 mg, 3 mmol) was dissolved in glacial acetic acid (4.5 ml) and hot water (7 ml). Sodium cyanate (195 mg, 3 mmol) dissolved in hot water (5 ml) was added dropwise with stirring. After precipitation of 4-biphenylurea, the reaction mixture was cooled in an ice bath, filtered and dried (98%). The product was recrystallized from ethyl acetate (m.p. 446–448 K).

Refinement top

H atoms of phenyl groups were fixed (riding on their C atoms) and H atoms bonded to nitrogen were refined isotropically.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: Scalepak (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLUTON (Spek, 1992); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. ORTEPII (Johnson, 1976) diagram and atom-numbering scheme for (I); displacement ellipsoids are drawn at 50% probability level for non-H atoms.
[Figure 2] Fig. 2. Packing diagram of (I) to show the N—H(anti)···O hydrogen bonded α network along [100] and the N—H(syn)···π interaction. Interdigitation of biphenyl groups is not shown for clarity.
4-Biphenylylurea top
Crystal data top
C13H12N2ODx = 1.318 Mg m3
Dm = 1.293 Mg m3
Dm measured by not measured
Mr = 212.25Melting point: 446-448 K K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 14801 reflections
a = 9.3700 (4) Åθ = 2.9–27.5°
b = 13.0330 (5) ŵ = 0.09 mm1
c = 17.5210 (6) ÅT = 123 K
V = 2139.7 (1) Å3Prisms, colourless
Z = 80.34 × 0.30 × 0.23 mm
F(000) = 896
Data collection top
Nonius Kappa CCD
diffractometer
1964 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.029
Graphite monochromatorθmax = 27.5°, θmin = 2.9°
ω–scansh = 129
10130 measured reflectionsk = 1316
2436 independent reflectionsl = 2219
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.049P)2 + 0.7752P]
where P = (Fo2 + 2Fc2)/3
2436 reflections(Δ/σ)max = 0.029
157 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C13H12N2OV = 2139.7 (1) Å3
Mr = 212.25Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 9.3700 (4) ŵ = 0.09 mm1
b = 13.0330 (5) ÅT = 123 K
c = 17.5210 (6) Å0.34 × 0.30 × 0.23 mm
Data collection top
Nonius Kappa CCD
diffractometer
1964 reflections with I > 2σ(I)
10130 measured reflectionsRint = 0.029
2436 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.24 e Å3
2436 reflectionsΔρmin = 0.20 e Å3
157 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 on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating R_factor(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
xyzUiso*/Ueq
O10.09302 (10)0.38606 (7)0.22197 (5)0.0318 (2)
N130.13751 (12)0.44387 (9)0.21879 (6)0.0254 (3)
N150.08108 (14)0.29902 (10)0.28721 (7)0.0341 (3)
C120.02170 (13)0.62435 (9)0.06599 (7)0.0256 (3)
H12A0.050240.631260.029780.031*
C110.01861 (13)0.54120 (10)0.11561 (7)0.0254 (3)
H11A0.054770.493340.112490.030*
C100.12575 (13)0.52978 (9)0.17000 (7)0.0232 (3)
C140.03360 (13)0.37785 (9)0.24112 (7)0.0241 (3)
C90.23309 (13)0.60366 (10)0.17471 (7)0.0261 (3)
H9A0.304250.597280.211400.031*
C70.12988 (13)0.69770 (9)0.06909 (7)0.0235 (3)
C60.13492 (12)0.78520 (10)0.01452 (7)0.0237 (3)
C50.16329 (13)0.88472 (10)0.03978 (8)0.0268 (3)
H5A0.178780.896560.091470.032*
C80.23452 (13)0.68651 (10)0.12513 (7)0.0257 (3)
H8A0.306370.735420.129270.031*
C40.16871 (14)0.96593 (10)0.01086 (8)0.0304 (3)
H4A0.187471.031800.006920.036*
C30.14628 (14)0.94947 (11)0.08793 (8)0.0319 (3)
H3A0.149721.004160.121980.038*
C10.11267 (14)0.76948 (10)0.06350 (8)0.0295 (3)
H1A0.093720.703760.081550.035*
C20.11862 (15)0.85105 (12)0.11422 (8)0.0331 (3)
H2A0.104020.839740.166050.040*
H13A0.2201 (17)0.4320 (11)0.2376 (8)0.027 (4)*
H15B0.181 (2)0.2934 (13)0.2984 (10)0.048 (5)*
H15A0.014 (2)0.2528 (16)0.3082 (12)0.064 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0213 (5)0.0386 (6)0.0354 (5)0.0003 (4)0.0040 (4)0.0019 (4)
N130.0200 (6)0.0297 (6)0.0264 (6)0.0010 (4)0.0016 (4)0.0042 (5)
N150.0330 (7)0.0339 (7)0.0353 (7)0.0015 (5)0.0027 (5)0.0072 (5)
C120.0236 (6)0.0277 (7)0.0254 (6)0.0013 (5)0.0048 (5)0.0027 (5)
C110.0214 (6)0.0254 (6)0.0292 (7)0.0025 (5)0.0021 (5)0.0019 (5)
C100.0225 (6)0.0252 (6)0.0219 (6)0.0018 (5)0.0026 (5)0.0012 (5)
C140.0243 (6)0.0270 (6)0.0211 (6)0.0011 (5)0.0055 (5)0.0037 (5)
C90.0225 (6)0.0311 (7)0.0246 (6)0.0004 (5)0.0046 (5)0.0014 (5)
C70.0241 (6)0.0241 (6)0.0222 (6)0.0008 (5)0.0009 (5)0.0041 (5)
C60.0197 (6)0.0276 (6)0.0238 (6)0.0003 (5)0.0003 (5)0.0006 (5)
C50.0253 (6)0.0290 (7)0.0262 (6)0.0010 (5)0.0005 (5)0.0018 (5)
C80.0236 (6)0.0271 (7)0.0263 (6)0.0041 (5)0.0015 (5)0.0022 (5)
C40.0261 (7)0.0266 (7)0.0384 (8)0.0014 (5)0.0003 (6)0.0009 (6)
C30.0249 (7)0.0357 (7)0.0350 (7)0.0012 (6)0.0016 (5)0.0107 (6)
C10.0314 (7)0.0300 (7)0.0270 (7)0.0010 (6)0.0012 (5)0.0031 (5)
C20.0301 (7)0.0450 (8)0.0242 (7)0.0010 (6)0.0011 (5)0.0029 (6)
Geometric parameters (Å, º) top
O1—C141.238 (2)C7—C81.395 (2)
N13—C141.357 (2)C7—C61.489 (2)
N13—C101.413 (2)C6—C51.396 (2)
N13—H13A0.86 (2)C6—C11.398 (2)
N15—C141.380 (2)C5—C41.382 (2)
N15—H15B0.96 (2)C5—H5A0.93
N15—H15A0.94 (2)C8—H8A0.93
C12—C111.390 (2)C4—C31.383 (2)
C12—C71.394 (2)C4—H4A0.93
C12—H12A0.93C3—C21.387 (2)
C11—C101.392 (2)C3—H3A0.93
C11—H11A0.93C1—C21.387 (2)
C10—C91.395 (2)C1—H1A0.93
C9—C81.386 (2)C2—H2A0.93
C9—H9A0.93
C14—N13—C10128.38 (11)C12—C7—C6121.54 (11)
C14—N13—H13A115.1 (10)C5—C6—C1118.33 (12)
C10—N13—H13A116.5 (10)C5—C6—C7120.94 (11)
C14—N15—H15B119.4 (10)C1—C6—C7120.73 (11)
C14—N15—H15A119.3 (13)C4—C5—C6121.00 (12)
H15B—N15—H15A121.2 (16)C4—C5—H5A119.50 (8)
C11—C12—C7121.69 (12)C6—C5—H5A119.50 (8)
C11—C12—H12A119.15 (7)C9—C8—C7121.05 (12)
C7—C12—H12A119.15 (7)C9—C8—H8A119.47 (7)
C12—C11—C10119.78 (11)C7—C8—H8A119.47 (7)
C12—C11—H11A120.11 (7)C5—C4—C3120.16 (13)
C10—C11—H11A120.11 (7)C5—C4—H4A119.92 (8)
C11—C10—C9119.12 (11)C3—C4—H4A119.92 (8)
C11—C10—N13123.72 (11)C4—C3—C2119.73 (13)
C9—C10—N13117.06 (11)C4—C3—H3A120.14 (8)
O1—C14—N13123.71 (12)C2—C3—H3A120.14 (8)
O1—C14—N15122.13 (12)C2—C1—C6120.55 (13)
N13—C14—N15114.16 (12)C2—C1—H1A119.73 (8)
C8—C9—C10120.51 (12)C6—C1—H1A119.73 (8)
C8—C9—H9A119.74 (7)C1—C2—C3120.24 (13)
C10—C9—H9A119.74 (7)C1—C2—H2A119.88 (8)
C8—C7—C12117.81 (12)C3—C2—H2A119.88 (8)
C8—C7—C6120.64 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N13—H13A···O1i0.855 (16)1.982 (16)2.8320 (16)172.8 (14)
N15—H15B···O1i0.959 (19)2.464 (18)3.2615 (18)140.5 (14)
N15—H15A···πii0.95 (2)2.573.503169.0
Symmetry codes: (i) x1/2, y, z+1/2; (ii) x, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC13H12N2O
Mr212.25
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)123
a, b, c (Å)9.3700 (4), 13.0330 (5), 17.5210 (6)
V3)2139.7 (1)
Z8
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.34 × 0.30 × 0.23
Data collection
DiffractometerNonius Kappa CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
10130, 2436, 1964
Rint0.029
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.097, 1.02
No. of reflections2436
No. of parameters157
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.24, 0.20

Computer programs: COLLECT (Nonius, 1998), DENZO-SMN (Otwinowski & Minor, 1997), Scalepak (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976) and PLUTON (Spek, 1992), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N13—H13A···O1i.855 (16)1.982 (16)2.8320 (16)172.8 (14)
N15—H15B···O1i.959 (19)2.464 (18)3.2615 (18)140.5 (14)
N15—H15A···πii.95 (2)2.573.503169.0
Symmetry codes: (i) x1/2, y, z+1/2; (ii) x, y1/2, z+1/2.
 

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