Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101005807/jz1458sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101005807/jz1458Isup2.hkl |
CCDC reference: 167007
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).
H atoms of phenyl groups were fixed (riding on their C atoms) and H atoms bonded to nitrogen were refined isotropically.
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.
C13H12N2O | Dx = 1.318 Mg m−3 Dm = 1.293 Mg m−3 Dm measured by not measured |
Mr = 212.25 | Melting point: 446-448 K K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 14801 reflections |
a = 9.3700 (4) Å | θ = 2.9–27.5° |
b = 13.0330 (5) Å | µ = 0.09 mm−1 |
c = 17.5210 (6) Å | T = 123 K |
V = 2139.7 (1) Å3 | Prisms, colourless |
Z = 8 | 0.34 × 0.30 × 0.23 mm |
F(000) = 896 |
Nonius Kappa CCD diffractometer | 1964 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.029 |
Graphite monochromator | θmax = 27.5°, θmin = 2.9° |
ω–scans | h = −12→9 |
10130 measured reflections | k = −13→16 |
2436 independent reflections | l = −22→19 |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | H 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 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C13H12N2O | V = 2139.7 (1) Å3 |
Mr = 212.25 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 9.3700 (4) Å | µ = 0.09 mm−1 |
b = 13.0330 (5) Å | T = 123 K |
c = 17.5210 (6) Å | 0.34 × 0.30 × 0.23 mm |
Nonius Kappa CCD diffractometer | 1964 reflections with I > 2σ(I) |
10130 measured reflections | Rint = 0.029 |
2436 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.097 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.24 e Å−3 |
2436 reflections | Δρmin = −0.20 e Å−3 |
157 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.09302 (10) | 0.38606 (7) | 0.22197 (5) | 0.0318 (2) | |
N13 | −0.13751 (12) | 0.44387 (9) | 0.21879 (6) | 0.0254 (3) | |
N15 | −0.08108 (14) | 0.29902 (10) | 0.28721 (7) | 0.0341 (3) | |
C12 | −0.02170 (13) | 0.62435 (9) | 0.06599 (7) | 0.0256 (3) | |
H12A | 0.05024 | 0.63126 | 0.02978 | 0.031* | |
C11 | −0.01861 (13) | 0.54120 (10) | 0.11561 (7) | 0.0254 (3) | |
H11A | 0.05477 | 0.49334 | 0.11249 | 0.030* | |
C10 | −0.12575 (13) | 0.52978 (9) | 0.17000 (7) | 0.0232 (3) | |
C14 | −0.03360 (13) | 0.37785 (9) | 0.24112 (7) | 0.0241 (3) | |
C9 | −0.23309 (13) | 0.60366 (10) | 0.17471 (7) | 0.0261 (3) | |
H9A | −0.30425 | 0.59728 | 0.21140 | 0.031* | |
C7 | −0.12988 (13) | 0.69770 (9) | 0.06909 (7) | 0.0235 (3) | |
C6 | −0.13492 (12) | 0.78520 (10) | 0.01452 (7) | 0.0237 (3) | |
C5 | −0.16329 (13) | 0.88472 (10) | 0.03978 (8) | 0.0268 (3) | |
H5A | −0.17878 | 0.89656 | 0.09147 | 0.032* | |
C8 | −0.23452 (13) | 0.68651 (10) | 0.12513 (7) | 0.0257 (3) | |
H8A | −0.30637 | 0.73542 | 0.12927 | 0.031* | |
C4 | −0.16871 (14) | 0.96593 (10) | −0.01086 (8) | 0.0304 (3) | |
H4A | −0.18747 | 1.03180 | 0.00692 | 0.036* | |
C3 | −0.14628 (14) | 0.94947 (11) | −0.08793 (8) | 0.0319 (3) | |
H3A | −0.14972 | 1.00416 | −0.12198 | 0.038* | |
C1 | −0.11267 (14) | 0.76948 (10) | −0.06350 (8) | 0.0295 (3) | |
H1A | −0.09372 | 0.70376 | −0.08155 | 0.035* | |
C2 | −0.11862 (15) | 0.85105 (12) | −0.11422 (8) | 0.0331 (3) | |
H2A | −0.10402 | 0.83974 | −0.16605 | 0.040* | |
H13A | −0.2201 (17) | 0.4320 (11) | 0.2376 (8) | 0.027 (4)* | |
H15B | −0.181 (2) | 0.2934 (13) | 0.2984 (10) | 0.048 (5)* | |
H15A | −0.014 (2) | 0.2528 (16) | 0.3082 (12) | 0.064 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0213 (5) | 0.0386 (6) | 0.0354 (5) | −0.0003 (4) | −0.0040 (4) | 0.0019 (4) |
N13 | 0.0200 (6) | 0.0297 (6) | 0.0264 (6) | −0.0010 (4) | 0.0016 (4) | 0.0042 (5) |
N15 | 0.0330 (7) | 0.0339 (7) | 0.0353 (7) | −0.0015 (5) | −0.0027 (5) | 0.0072 (5) |
C12 | 0.0236 (6) | 0.0277 (7) | 0.0254 (6) | −0.0013 (5) | 0.0048 (5) | −0.0027 (5) |
C11 | 0.0214 (6) | 0.0254 (6) | 0.0292 (7) | 0.0025 (5) | 0.0021 (5) | −0.0019 (5) |
C10 | 0.0225 (6) | 0.0252 (6) | 0.0219 (6) | −0.0018 (5) | −0.0026 (5) | −0.0012 (5) |
C14 | 0.0243 (6) | 0.0270 (6) | 0.0211 (6) | −0.0011 (5) | −0.0055 (5) | −0.0037 (5) |
C9 | 0.0225 (6) | 0.0311 (7) | 0.0246 (6) | 0.0004 (5) | 0.0046 (5) | −0.0014 (5) |
C7 | 0.0241 (6) | 0.0241 (6) | 0.0222 (6) | −0.0008 (5) | −0.0009 (5) | −0.0041 (5) |
C6 | 0.0197 (6) | 0.0276 (6) | 0.0238 (6) | −0.0003 (5) | −0.0003 (5) | −0.0006 (5) |
C5 | 0.0253 (6) | 0.0290 (7) | 0.0262 (6) | 0.0010 (5) | 0.0005 (5) | −0.0018 (5) |
C8 | 0.0236 (6) | 0.0271 (7) | 0.0263 (6) | 0.0041 (5) | 0.0015 (5) | −0.0022 (5) |
C4 | 0.0261 (7) | 0.0266 (7) | 0.0384 (8) | 0.0014 (5) | −0.0003 (6) | 0.0009 (6) |
C3 | 0.0249 (7) | 0.0357 (7) | 0.0350 (7) | −0.0012 (6) | −0.0016 (5) | 0.0107 (6) |
C1 | 0.0314 (7) | 0.0300 (7) | 0.0270 (7) | 0.0010 (6) | 0.0012 (5) | −0.0031 (5) |
C2 | 0.0301 (7) | 0.0450 (8) | 0.0242 (7) | −0.0010 (6) | 0.0011 (5) | 0.0029 (6) |
O1—C14 | 1.238 (2) | C7—C8 | 1.395 (2) |
N13—C14 | 1.357 (2) | C7—C6 | 1.489 (2) |
N13—C10 | 1.413 (2) | C6—C5 | 1.396 (2) |
N13—H13A | 0.86 (2) | C6—C1 | 1.398 (2) |
N15—C14 | 1.380 (2) | C5—C4 | 1.382 (2) |
N15—H15B | 0.96 (2) | C5—H5A | 0.93 |
N15—H15A | 0.94 (2) | C8—H8A | 0.93 |
C12—C11 | 1.390 (2) | C4—C3 | 1.383 (2) |
C12—C7 | 1.394 (2) | C4—H4A | 0.93 |
C12—H12A | 0.93 | C3—C2 | 1.387 (2) |
C11—C10 | 1.392 (2) | C3—H3A | 0.93 |
C11—H11A | 0.93 | C1—C2 | 1.387 (2) |
C10—C9 | 1.395 (2) | C1—H1A | 0.93 |
C9—C8 | 1.386 (2) | C2—H2A | 0.93 |
C9—H9A | 0.93 | ||
C14—N13—C10 | 128.38 (11) | C12—C7—C6 | 121.54 (11) |
C14—N13—H13A | 115.1 (10) | C5—C6—C1 | 118.33 (12) |
C10—N13—H13A | 116.5 (10) | C5—C6—C7 | 120.94 (11) |
C14—N15—H15B | 119.4 (10) | C1—C6—C7 | 120.73 (11) |
C14—N15—H15A | 119.3 (13) | C4—C5—C6 | 121.00 (12) |
H15B—N15—H15A | 121.2 (16) | C4—C5—H5A | 119.50 (8) |
C11—C12—C7 | 121.69 (12) | C6—C5—H5A | 119.50 (8) |
C11—C12—H12A | 119.15 (7) | C9—C8—C7 | 121.05 (12) |
C7—C12—H12A | 119.15 (7) | C9—C8—H8A | 119.47 (7) |
C12—C11—C10 | 119.78 (11) | C7—C8—H8A | 119.47 (7) |
C12—C11—H11A | 120.11 (7) | C5—C4—C3 | 120.16 (13) |
C10—C11—H11A | 120.11 (7) | C5—C4—H4A | 119.92 (8) |
C11—C10—C9 | 119.12 (11) | C3—C4—H4A | 119.92 (8) |
C11—C10—N13 | 123.72 (11) | C4—C3—C2 | 119.73 (13) |
C9—C10—N13 | 117.06 (11) | C4—C3—H3A | 120.14 (8) |
O1—C14—N13 | 123.71 (12) | C2—C3—H3A | 120.14 (8) |
O1—C14—N15 | 122.13 (12) | C2—C1—C6 | 120.55 (13) |
N13—C14—N15 | 114.16 (12) | C2—C1—H1A | 119.73 (8) |
C8—C9—C10 | 120.51 (12) | C6—C1—H1A | 119.73 (8) |
C8—C9—H9A | 119.74 (7) | C1—C2—C3 | 120.24 (13) |
C10—C9—H9A | 119.74 (7) | C1—C2—H2A | 119.88 (8) |
C8—C7—C12 | 117.81 (12) | C3—C2—H2A | 119.88 (8) |
C8—C7—C6 | 120.64 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
N13—H13A···O1i | 0.855 (16) | 1.982 (16) | 2.8320 (16) | 172.8 (14) |
N15—H15B···O1i | 0.959 (19) | 2.464 (18) | 3.2615 (18) | 140.5 (14) |
N15—H15A···πii | 0.95 (2) | 2.57 | 3.503 | 169.0 |
Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) −x, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C13H12N2O |
Mr | 212.25 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 123 |
a, b, c (Å) | 9.3700 (4), 13.0330 (5), 17.5210 (6) |
V (Å3) | 2139.7 (1) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.34 × 0.30 × 0.23 |
Data collection | |
Diffractometer | Nonius Kappa CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10130, 2436, 1964 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.097, 1.02 |
No. of reflections | 2436 |
No. of parameters | 157 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 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.
D—H···A | D—H | H···A | D···A | D—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) | 2.57 | 3.503 | 169.0 |
Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) −x, y−1/2, −z+1/2. |
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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.