supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

rz2236 scheme

Acta Cryst. (2008). E64, o1698    [ doi:10.1107/S1600536808024124 ]

(RS)-N-[(4-Chlorophenyl)(phenyl)methyl]formamide

Z.-H. Zou, Q.-Y. Wang and Z.-S. Li

Abstract top

The racemic title compound, C14H12ClNO, contains two molecules in the asymmetric unit. The dihedral angles between the phenyl and benzene rings are 84.03 (15) and 83.92 (13)°. The crystal structure involves intermolecular N-H...O, C-H...Cl and C-H...O hydrogen bonds, linking molecules into layers parallel to the (100) plane.

Comment top

As part of our ongoing investigations on the asymmetric synthesis, the title compound, C14H12ClNO, has been obtained as a racemic mixture and structurally characterized. The compound is the key intermediate for the synthesis of levocetirizine dihydrochloride (Pflum et al., 2002; Wang et al., 2007), a high effective non-sedating H1 receptor antagonist for the treatment of allergic diseases (Wang et al., 2005). The asymmetric unit of the title compound (Fig. 1) contains two molecules. The dihedral angles formed by planes of the phenyl and benzene rings are 84.03 (15) and 83.92 (13)°. In the crystal structure (Fig. 2), intermolecular N—H···O, C—H···Cl and C—H···O hydrogen bonds (Table 1) link molecules into layers parallel to the (100) plane.

Related literature top

For related literature, see: Pflum et al. (2002); Wang et al. (2005); , 2007).

Experimental top

All chemicals used (reagent grade) were commercially available. A mixture of (4-chlorophenyl)phenylmethanone (21.67 g) and formamide (18.02 g) was stirred at 180°C for 20 h. The mixture was cooled to room temperature, and the resulting precipitate was filtered off, washed with water and dried. Colourless crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of a 60% aqueous ethanol solution.

Refinement top

All H atoms were placed in calculated positions and refined using a riding model, with C—H = 0.93–0.98 Å, N—H = 0.86 Å, and with Uiso(H) = 1.2 Ueq(C, N).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. Crystal packing of the title compound viewed along the b axis. Hydrogen bonds are shown as dashed lines.
(RS)-N-[(4-Chlorophenyl)(phenyl)methyl]formamide top
Crystal data top
C14H12ClNOF000 = 1024
Mr = 245.70Dx = 1.297 Mg m−3
Monoclinic, P21/cMelting point: 397(2) K
Hall symbol: -P 2ybcMo Kα radiation
λ = 0.71073 Å
a = 16.830 (4) ÅCell parameters from 3463 reflections
b = 9.6318 (12) Åθ = 2.6–27.4º
c = 16.683 (4) ŵ = 0.29 mm−1
β = 111.538 (12)ºT = 293 (2) K
V = 2515.6 (9) Å3Prism, colourless
Z = 80.25 × 0.20 × 0.20 mm
Data collection top
Rigaku Scxmini CCD area-detector
diffractometer		4421 independent reflections
Radiation source: fine-focus sealed tube2499 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.079
Detector resolution: 8.192 pixels mm-1θmax = 25.0º
T = 293(2) Kθmin = 2.9º
Thin–slice ω scansh = −20→19
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = −11→11
Tmin = 0.852, Tmax = 0.940l = −19→19
20642 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.075H-atom parameters constrained
wR(F2) = 0.202  w = 1/[σ2(Fo2) + (0.0904P)2 + 0.5905P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
4421 reflectionsΔρmax = 0.73 e Å−3
307 parametersΔρmin = −0.36 e Å−3
72 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C14H12ClNOV = 2515.6 (9) Å3
Mr = 245.70Z = 8
Monoclinic, P21/cMo Kα
a = 16.830 (4) ŵ = 0.29 mm−1
b = 9.6318 (12) ÅT = 293 (2) K
c = 16.683 (4) Å0.25 × 0.20 × 0.20 mm
β = 111.538 (12)º
Data collection top
Rigaku Scxmini CCD area-detector
diffractometer		4421 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		2499 reflections with I > 2σ(I)
Tmin = 0.852, Tmax = 0.940Rint = 0.079
20642 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.07572 restraints
wR(F2) = 0.202H-atom parameters constrained
S = 1.06Δρmax = 0.73 e Å−3
4421 reflectionsΔρmin = −0.36 e Å−3
307 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
xyzUiso*/Ueq
Cl10.01712 (8)0.62109 (17)0.23035 (11)0.1079 (6)
N10.38686 (18)0.7588 (3)0.49582 (19)0.0507 (8)
H1A0.39330.81950.46090.061*
O10.43270 (19)0.6899 (3)0.63510 (18)0.0748 (9)
C10.1291 (3)0.8461 (5)0.4650 (3)0.0799 (8)
H1B0.10940.93710.46040.096*
C20.0808 (3)0.7419 (5)0.4757 (3)0.0792 (8)
C30.1074 (3)0.6102 (5)0.4809 (3)0.0794 (7)
H3A0.07320.53890.48790.095*
C40.1864 (3)0.5799 (5)0.4758 (3)0.0767 (7)
H4A0.20420.48800.47890.092*
C50.2386 (3)0.6838 (5)0.4664 (3)0.0734 (7)
C60.2087 (3)0.8181 (5)0.4607 (3)0.0768 (7)
H6A0.24210.89080.45400.092*
C70.3235 (2)0.6486 (4)0.4612 (2)0.0495 (10)
H7A0.34500.56630.49720.059*
C80.4345 (2)0.7687 (4)0.5785 (3)0.0556 (10)
H8A0.47280.84240.59510.067*
C90.3201 (2)0.6125 (4)0.3711 (2)0.0497 (9)
C100.3871 (3)0.5419 (4)0.3602 (3)0.0613 (11)
H10A0.43300.51370.40860.074*
C110.3875 (3)0.5125 (4)0.2798 (3)0.0693 (12)
H11A0.43340.46540.27410.083*
C120.3200 (3)0.5526 (5)0.2079 (3)0.0680 (12)
H12A0.32080.53400.15350.082*
C130.2516 (3)0.6198 (5)0.2156 (3)0.0685 (12)
H13A0.20570.64550.16660.082*
C140.2510 (3)0.6495 (4)0.2969 (3)0.0591 (11)
H14A0.20420.69440.30210.071*
C15−0.3219 (2)0.6980 (3)0.3572 (2)0.0422 (8)
C16−0.3975 (3)0.7165 (5)0.3709 (3)0.0633 (12)
H16A−0.44860.68700.32920.076*
C17−0.3984 (3)0.7773 (5)0.4448 (3)0.0763 (14)
H17A−0.45010.78850.45240.092*
C18−0.3243 (3)0.8218 (5)0.5075 (3)0.0727 (13)
H18A−0.32520.86280.55760.087*
C19−0.2489 (3)0.8050 (4)0.4951 (3)0.0650 (12)
H19A−0.19820.83540.53700.078*
C20−0.2474 (2)0.7433 (4)0.4207 (2)0.0520 (10)
H20A−0.19550.73220.41340.062*
C21−0.3933 (2)0.4215 (4)0.1961 (3)0.0481 (9)
H21A−0.41620.33420.19770.058*
C22−0.3231 (2)0.6294 (4)0.2750 (2)0.0419 (8)
H22A−0.36160.68380.22680.050*
C23−0.2370 (2)0.6242 (4)0.2647 (2)0.0433 (9)
C24−0.1850 (3)0.5092 (4)0.2863 (3)0.0621 (11)
H24A−0.20260.43080.30770.074*
C25−0.1066 (3)0.5083 (5)0.2765 (3)0.0737 (13)
H25A−0.07210.42980.29110.088*
C26−0.0805 (3)0.6240 (5)0.2453 (3)0.0634 (12)
C27−0.1291 (3)0.7407 (5)0.2256 (3)0.0660 (12)
H27A−0.11010.81980.20620.079*
C28−0.2075 (3)0.7400 (4)0.2349 (2)0.0553 (10)
H28A−0.24130.81930.22080.066*
Cl2−0.01756 (10)0.7788 (3)0.48385 (13)0.1502 (9)
O2−0.39511 (18)0.4638 (3)0.12630 (16)0.0611 (8)
N2−0.36098 (19)0.4909 (3)0.26976 (19)0.0489 (8)
H2A−0.36230.45340.31600.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0730 (8)0.1320 (13)0.1412 (13)−0.0120 (8)0.0659 (9)−0.0164 (10)
N10.0546 (19)0.051 (2)0.0450 (18)−0.0095 (16)0.0168 (15)0.0059 (16)
O10.079 (2)0.092 (2)0.0515 (17)−0.0125 (17)0.0221 (15)0.0154 (17)
C10.0672 (14)0.0827 (15)0.0949 (16)−0.0086 (13)0.0356 (13)−0.0070 (14)
C20.0665 (14)0.0854 (15)0.0928 (16)−0.0105 (13)0.0375 (13)−0.0053 (14)
C30.0674 (14)0.0848 (15)0.0928 (15)−0.0139 (13)0.0374 (13)−0.0011 (14)
C40.0661 (14)0.0805 (15)0.0910 (15)−0.0132 (13)0.0376 (13)−0.0005 (14)
C50.0638 (14)0.0766 (15)0.0887 (15)−0.0119 (12)0.0385 (13)−0.0025 (14)
C60.0653 (14)0.0789 (15)0.0929 (16)−0.0101 (13)0.0369 (13)−0.0053 (14)
C70.054 (2)0.045 (2)0.048 (2)−0.0030 (18)0.0159 (18)0.0099 (18)
C80.052 (2)0.065 (3)0.051 (2)−0.010 (2)0.021 (2)−0.001 (2)
C90.053 (2)0.036 (2)0.060 (2)−0.0040 (18)0.0203 (19)0.0036 (19)
C100.056 (3)0.051 (2)0.074 (3)0.002 (2)0.020 (2)−0.005 (2)
C110.066 (3)0.059 (3)0.089 (3)−0.001 (2)0.036 (3)−0.018 (3)
C120.089 (3)0.060 (3)0.061 (3)−0.018 (3)0.035 (3)−0.023 (2)
C130.075 (3)0.066 (3)0.060 (3)0.001 (2)0.019 (2)−0.002 (2)
C140.060 (3)0.058 (3)0.060 (3)0.008 (2)0.023 (2)0.001 (2)
C150.052 (2)0.0359 (19)0.0396 (19)−0.0002 (17)0.0179 (17)−0.0014 (16)
C160.054 (3)0.080 (3)0.059 (3)0.003 (2)0.025 (2)−0.011 (2)
C170.076 (3)0.092 (4)0.072 (3)0.015 (3)0.041 (3)−0.010 (3)
C180.107 (4)0.066 (3)0.053 (3)0.021 (3)0.039 (3)−0.007 (2)
C190.077 (3)0.066 (3)0.049 (2)0.006 (2)0.019 (2)−0.011 (2)
C200.057 (2)0.051 (2)0.049 (2)0.0010 (19)0.0214 (19)−0.0039 (19)
C210.052 (2)0.041 (2)0.055 (2)−0.0070 (18)0.0234 (19)−0.007 (2)
C220.049 (2)0.039 (2)0.0384 (19)−0.0052 (17)0.0163 (16)−0.0016 (16)
C230.054 (2)0.041 (2)0.0353 (18)−0.0042 (18)0.0162 (16)−0.0037 (17)
C240.064 (3)0.047 (2)0.083 (3)0.004 (2)0.037 (2)0.005 (2)
C250.061 (3)0.061 (3)0.107 (4)0.007 (2)0.040 (3)−0.006 (3)
C260.056 (2)0.075 (3)0.069 (3)−0.013 (2)0.035 (2)−0.017 (3)
C270.069 (3)0.074 (3)0.066 (3)−0.015 (3)0.037 (2)0.001 (2)
C280.065 (3)0.047 (2)0.060 (2)−0.001 (2)0.029 (2)0.008 (2)
Cl20.0714 (9)0.235 (2)0.1627 (17)−0.0194 (12)0.0645 (10)−0.0648 (16)
O20.086 (2)0.0561 (17)0.0452 (16)−0.0077 (15)0.0283 (15)−0.0078 (14)
N20.063 (2)0.0477 (19)0.0403 (17)−0.0097 (16)0.0237 (15)−0.0029 (15)
Geometric parameters (Å, °) top
Cl1—C261.751 (4)C14—H14A0.9300
N1—C81.320 (5)C15—C201.382 (5)
N1—C71.464 (4)C15—C161.385 (5)
N1—H1A0.8600C15—C221.514 (5)
O1—C81.220 (4)C16—C171.369 (6)
C1—C21.345 (6)C16—H16A0.9300
C1—C61.394 (6)C17—C181.371 (6)
C1—H1B0.9300C17—H17A0.9300
C2—C31.337 (7)C18—C191.368 (6)
C2—Cl21.746 (5)C18—H18A0.9300
C3—C41.394 (6)C19—C201.385 (5)
C3—H3A0.9300C19—H19A0.9300
C4—C51.378 (6)C20—H20A0.9300
C4—H4A0.9300C21—O21.224 (4)
C5—C61.378 (6)C21—N21.327 (4)
C5—C71.502 (6)C21—H21A0.9300
C6—H6A0.9300C22—N21.467 (4)
C7—C91.523 (5)C22—C231.521 (5)
C7—H7A0.9800C22—H22A0.9800
C8—H8A0.9300C23—C241.375 (5)
C9—C101.385 (5)C23—C281.385 (5)
C9—C141.397 (5)C24—C251.387 (6)
C10—C111.373 (6)C24—H24A0.9300
C10—H10A0.9300C25—C261.368 (6)
C11—C121.370 (6)C25—H25A0.9300
C11—H11A0.9300C26—C271.358 (6)
C12—C131.367 (6)C27—C281.385 (5)
C12—H12A0.9300C27—H27A0.9300
C13—C141.390 (6)C28—H28A0.9300
C13—H13A0.9300N2—H2A0.8600
C8—N1—C7122.6 (3)C20—C15—C16117.5 (3)
C8—N1—H1A118.7C20—C15—C22122.6 (3)
C7—N1—H1A118.7C16—C15—C22119.8 (3)
C2—C1—C6120.1 (5)C17—C16—C15121.3 (4)
C2—C1—H1B119.9C17—C16—H16A119.4
C6—C1—H1B119.9C15—C16—H16A119.4
C3—C2—C1120.7 (5)C16—C17—C18120.9 (4)
C3—C2—Cl2119.5 (4)C16—C17—H17A119.6
C1—C2—Cl2119.7 (4)C18—C17—H17A119.6
C2—C3—C4120.0 (4)C19—C18—C17118.8 (4)
C2—C3—H3A120.0C19—C18—H18A120.6
C4—C3—H3A120.0C17—C18—H18A120.6
C5—C4—C3121.1 (5)C18—C19—C20120.7 (4)
C5—C4—H4A119.4C18—C19—H19A119.7
C3—C4—H4A119.4C20—C19—H19A119.7
C4—C5—C6117.2 (4)C15—C20—C19120.9 (4)
C4—C5—C7120.2 (4)C15—C20—H20A119.6
C6—C5—C7122.6 (4)C19—C20—H20A119.6
C5—C6—C1120.8 (4)O2—C21—N2124.9 (3)
C5—C6—H6A119.6O2—C21—H21A117.6
C1—C6—H6A119.6N2—C21—H21A117.6
N1—C7—C5112.6 (3)N2—C22—C15108.2 (3)
N1—C7—C9108.2 (3)N2—C22—C23112.0 (3)
C5—C7—C9114.6 (3)C15—C22—C23114.8 (3)
N1—C7—H7A107.0N2—C22—H22A107.2
C5—C7—H7A107.0C15—C22—H22A107.2
C9—C7—H7A107.0C23—C22—H22A107.2
O1—C8—N1125.9 (4)C24—C23—C28117.7 (4)
O1—C8—H8A117.1C24—C23—C22122.6 (3)
N1—C8—H8A117.1C28—C23—C22119.7 (3)
C10—C9—C14117.5 (4)C23—C24—C25121.1 (4)
C10—C9—C7120.3 (3)C23—C24—H24A119.5
C14—C9—C7122.2 (3)C25—C24—H24A119.5
C11—C10—C9121.7 (4)C26—C25—C24119.4 (4)
C11—C10—H10A119.2C26—C25—H25A120.3
C9—C10—H10A119.2C24—C25—H25A120.3
C12—C11—C10119.8 (4)C27—C26—C25121.2 (4)
C12—C11—H11A120.1C27—C26—Cl1119.5 (3)
C10—C11—H11A120.1C25—C26—Cl1119.4 (4)
C13—C12—C11120.5 (4)C26—C27—C28118.8 (4)
C13—C12—H12A119.8C26—C27—H27A120.6
C11—C12—H12A119.8C28—C27—H27A120.6
C12—C13—C14119.8 (4)C27—C28—C23121.8 (4)
C12—C13—H13A120.1C27—C28—H28A119.1
C14—C13—H13A120.1C23—C28—H28A119.1
C13—C14—C9120.6 (4)C21—N2—C22122.3 (3)
C13—C14—H14A119.7C21—N2—H2A118.8
C9—C14—H14A119.7C22—N2—H2A118.8
C6—C1—C2—C3−1.2 (8)C20—C15—C16—C170.0 (6)
C6—C1—C2—Cl2178.3 (4)C22—C15—C16—C17179.5 (4)
C1—C2—C3—C40.5 (8)C15—C16—C17—C180.0 (7)
Cl2—C2—C3—C4−179.0 (4)C16—C17—C18—C190.2 (7)
C2—C3—C4—C50.7 (7)C17—C18—C19—C20−0.4 (7)
C3—C4—C5—C6−1.1 (7)C16—C15—C20—C19−0.1 (6)
C3—C4—C5—C7179.9 (4)C22—C15—C20—C19−179.7 (4)
C4—C5—C6—C10.4 (7)C18—C19—C20—C150.4 (6)
C7—C5—C6—C1179.3 (4)C20—C15—C22—N2121.4 (4)
C2—C1—C6—C50.8 (8)C16—C15—C22—N2−58.2 (4)
C8—N1—C7—C585.7 (4)C20—C15—C22—C23−4.5 (5)
C8—N1—C7—C9−146.6 (3)C16—C15—C22—C23176.0 (3)
C4—C5—C7—N1−149.9 (4)N2—C22—C23—C24−26.9 (5)
C6—C5—C7—N131.2 (6)C15—C22—C23—C2497.0 (4)
C4—C5—C7—C985.8 (5)N2—C22—C23—C28155.0 (3)
C6—C5—C7—C9−93.1 (5)C15—C22—C23—C28−81.1 (4)
C7—N1—C8—O10.6 (6)C28—C23—C24—C25−1.5 (6)
N1—C7—C9—C1071.5 (4)C22—C23—C24—C25−179.6 (4)
C5—C7—C9—C10−161.9 (4)C23—C24—C25—C260.3 (7)
N1—C7—C9—C14−107.9 (4)C24—C25—C26—C271.5 (7)
C5—C7—C9—C1418.7 (5)C24—C25—C26—Cl1−178.3 (3)
C14—C9—C10—C112.0 (6)C25—C26—C27—C28−2.0 (7)
C7—C9—C10—C11−177.5 (4)Cl1—C26—C27—C28177.8 (3)
C9—C10—C11—C12−0.4 (7)C26—C27—C28—C230.8 (6)
C10—C11—C12—C13−1.1 (7)C24—C23—C28—C270.9 (6)
C11—C12—C13—C141.0 (7)C22—C23—C28—C27179.1 (3)
C12—C13—C14—C90.6 (7)O2—C21—N2—C220.0 (6)
C10—C9—C14—C13−2.0 (6)C15—C22—N2—C21160.2 (3)
C7—C9—C14—C13177.4 (4)C23—C22—N2—C21−72.3 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.862.022.877 (4)174
N2—H2A···O1ii0.862.162.901 (4)144
C18—H18A···O2iii0.932.543.368 (5)148
C20—H20A···Cl20.932.823.633 (4)146
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, −y+1, −z+1; (iii) x, −y+3/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.862.022.877 (4)174
N2—H2A···O1ii0.862.162.901 (4)144
C18—H18A···O2iii0.932.543.368 (5)148
C20—H20A···Cl20.932.823.633 (4)146
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, −y+1, −z+1; (iii) x, −y+3/2, z+1/2.
Acknowledgements top

The authors thank Professor Sun Bai-Wang of Southeast University for help.

references
References top

Pflum, D. A., Krishnamurthy, D., Han, Z.-X., Wald, S. A. & Senanayake, C. H. (2002). Tetrahedron Lett. 43, 923–926.

Rigaku. (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Wang, Y.-L., Gao, Q.-S., Zhou, W. & Yan, S.-Z. (2005). Food Drugs, 7, 33–35.

Wang, L.-S., Wang, T.-W., Zhu, H.-Y. & Qiao, H.-Y. (2007). J. Guangxi Univ. 32, 384–385.