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In the title compound, C23H21Cl2NO, the five-membered oxazolidine ring has a half-boat conformation, with a dihedral angle of 37.4 (2)° between the C3O and C2N planes.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807022738/dn2169sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807022738/dn2169Isup2.hkl
Contains datablock I

CCDC reference: 651462

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.043
  • wR factor = 0.131
  • Data-to-parameter ratio = 18.6

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.60
Alert level G PLAT793_ALERT_1_G Check the Absolute Configuration of C3 = ... S
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

5-Chloromethyl-3-(3-chloro-2-methyl-phenyl)-2,2-diphenyl-oxazolidine, (I), was widely used as ligand for metal-catalyzed asymmetric synthesis (Agami et al., 2004). It was obtained from the reaction of 2-chloromethyl-oxirane and benzhydrylidene-(3-chloro-2-methyl- phenyl)-amine, as colorless crystals suitable for X-ray crystallographic analysis.

The molecular structure of (I) is built up from four rings, three of which are six-membered and one five-membered (Fig. 1). Atoms C1, C2, C3 and O1 are coplanar, the largest deviation being 0.0046 (10) Å for O1. Atom N1 deviates from the C1—C3/O1 plane by -0.5602 (23) Å. So the five membered oxazolidine ring has an half-boat conformation. The dihedral angles between the C1—C3/O1 plane and the C1/C3/N1 and C17—C22 planes are 37.42 (15)° and 89.86 (7)°, respectively. The dihedral angles between the C1—C3/O1 plane and the C5—C10 and C11—C16 planes are 69.24 (7)° and 26.39 (7)°, respectively. The molecule is chiral at C2 but as the space group is centrosymmetric, the unit cell contains the racemate (R,S).

Related literature top

For related literature, see: Agami & Couty (2004).

Experimental top

A mixture of 2-chloromethyl-oxirane (0.28 g, 3 mmol), benzhydrylidene-(3-chloro-2-methyl-phenyl)-amine (0.61 g, 2 mmol), and Yb(OTf)3 (0.06 g, 5 mol%) was stirred at 40°C for 4 h. After completion of conversion as indicated by TLC, the reaction mixture was purified by silica gel column chromatography with petroleum ether-ethyl acetate (10:1) as eluent to afford the white solid (0.72 g, 91%). A solution of the compound in ethanol was concentrated gradually at room temperature to afford colourless chunks (m.p. 379–380 K).

Refinement top

All H atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic), 0.97 Å (methylene), 0.96 Å (CH3) and 0.98 Å (methine) with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(CH3).

Structure description top

5-Chloromethyl-3-(3-chloro-2-methyl-phenyl)-2,2-diphenyl-oxazolidine, (I), was widely used as ligand for metal-catalyzed asymmetric synthesis (Agami et al., 2004). It was obtained from the reaction of 2-chloromethyl-oxirane and benzhydrylidene-(3-chloro-2-methyl- phenyl)-amine, as colorless crystals suitable for X-ray crystallographic analysis.

The molecular structure of (I) is built up from four rings, three of which are six-membered and one five-membered (Fig. 1). Atoms C1, C2, C3 and O1 are coplanar, the largest deviation being 0.0046 (10) Å for O1. Atom N1 deviates from the C1—C3/O1 plane by -0.5602 (23) Å. So the five membered oxazolidine ring has an half-boat conformation. The dihedral angles between the C1—C3/O1 plane and the C1/C3/N1 and C17—C22 planes are 37.42 (15)° and 89.86 (7)°, respectively. The dihedral angles between the C1—C3/O1 plane and the C5—C10 and C11—C16 planes are 69.24 (7)° and 26.39 (7)°, respectively. The molecule is chiral at C2 but as the space group is centrosymmetric, the unit cell contains the racemate (R,S).

For related literature, see: Agami & Couty (2004).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The structure of (I), shown with 30% probability displacement ellipsoids.
rac-5-Chloromethyl-3-(3-chloro-2-methylphenyl)-2,2-diphenyloxazolidine top
Crystal data top
C23H21Cl2NOF(000) = 1664
Mr = 398.31Dx = 1.315 Mg m3
Monoclinic, C2/cMelting point: 380 K
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 25.3638 (9) ÅCell parameters from 14749 reflections
b = 7.1591 (2) Åθ = 3.1–27.5°
c = 22.1688 (7) ŵ = 0.34 mm1
β = 91.263 (1)°T = 298 K
V = 4024.5 (2) Å3Chunk, colourless
Z = 80.53 × 0.48 × 0.39 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer
4564 independent reflections
Radiation source: fine-focus sealed tube3844 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
Detector resolution: 10.00 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω scansh = 3232
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 89
Tmin = 0.834, Tmax = 0.878l = 2828
18483 measured reflections
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0769P)2 + 1.6308P]
where P = (Fo2 + 2Fc2)/3
4564 reflections(Δ/σ)max = 0.046
245 parametersΔρmax = 0.70 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
C23H21Cl2NOV = 4024.5 (2) Å3
Mr = 398.31Z = 8
Monoclinic, C2/cMo Kα radiation
a = 25.3638 (9) ŵ = 0.34 mm1
b = 7.1591 (2) ÅT = 298 K
c = 22.1688 (7) Å0.53 × 0.48 × 0.39 mm
β = 91.263 (1)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer
4564 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
3844 reflections with I > 2σ(I)
Tmin = 0.834, Tmax = 0.878Rint = 0.021
18483 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.131H-atom parameters constrained
S = 1.06Δρmax = 0.70 e Å3
4564 reflectionsΔρmin = 0.27 e Å3
245 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
Cl10.023418 (19)0.76049 (8)0.46113 (2)0.06416 (17)
Cl20.06416 (2)0.14708 (7)0.14014 (2)0.06141 (16)
O10.12341 (4)0.69666 (16)0.40447 (6)0.0463 (3)
N10.10091 (5)0.42695 (18)0.35117 (5)0.0360 (3)
C10.14307 (6)0.5132 (2)0.38770 (7)0.0368 (3)
C20.05299 (6)0.4908 (2)0.38171 (8)0.0445 (4)
H2A0.04540.41200.41600.053*
H2B0.02270.49050.35420.053*
C30.06683 (7)0.6917 (3)0.40219 (9)0.0506 (4)
H30.05340.78150.37220.061*
C40.04747 (8)0.7428 (3)0.46360 (9)0.0607 (5)
H4A0.06270.86110.47620.073*
H4B0.05830.64820.49270.073*
C50.15366 (6)0.3955 (2)0.44474 (7)0.0395 (3)
C60.17638 (8)0.4769 (3)0.49598 (8)0.0564 (5)
H60.18190.60530.49710.068*
C70.19084 (9)0.3684 (4)0.54548 (8)0.0705 (6)
H70.20600.42470.57950.085*
C80.18294 (9)0.1788 (4)0.54477 (9)0.0669 (6)
H80.19290.10640.57800.080*
C90.16013 (9)0.0967 (3)0.49440 (9)0.0627 (5)
H90.15440.03150.49370.075*
C100.14575 (7)0.2039 (3)0.44476 (8)0.0498 (4)
H100.13060.14670.41100.060*
C110.19526 (6)0.5360 (2)0.35628 (6)0.0382 (3)
C120.22422 (7)0.7004 (3)0.36172 (8)0.0502 (4)
H120.21060.80180.38250.060*
C130.27367 (8)0.7123 (3)0.33595 (10)0.0606 (5)
H130.29310.82200.33970.073*
C140.29399 (7)0.5635 (3)0.30504 (8)0.0578 (5)
H140.32700.57280.28780.069*
C150.26552 (7)0.4008 (3)0.29954 (8)0.0549 (5)
H150.27920.30010.27850.066*
C160.21637 (6)0.3868 (3)0.32534 (7)0.0463 (4)
H160.19740.27600.32180.056*
C170.09890 (5)0.4577 (2)0.28690 (7)0.0355 (3)
C180.11064 (7)0.6283 (2)0.26038 (8)0.0474 (4)
H180.12020.72960.28450.057*
C190.10818 (8)0.6480 (3)0.19804 (9)0.0551 (4)
H190.11640.76230.18060.066*
C200.09367 (7)0.4997 (3)0.16203 (8)0.0502 (4)
H200.09210.51270.12030.060*
C210.08146 (6)0.3310 (2)0.18858 (7)0.0415 (3)
C220.08338 (5)0.3039 (2)0.25121 (7)0.0361 (3)
C230.07082 (8)0.1201 (2)0.28008 (8)0.0482 (4)
H23A0.06240.02980.24930.072*
H23B0.04120.13490.30590.072*
H23C0.10080.07780.30350.072*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0490 (3)0.0713 (3)0.0729 (3)0.0029 (2)0.0195 (2)0.0129 (2)
Cl20.0718 (3)0.0654 (3)0.0466 (2)0.0037 (2)0.0071 (2)0.0167 (2)
O10.0391 (6)0.0378 (6)0.0623 (7)0.0018 (5)0.0060 (5)0.0145 (5)
N10.0320 (6)0.0386 (6)0.0375 (6)0.0023 (5)0.0014 (5)0.0036 (5)
C10.0355 (7)0.0349 (7)0.0401 (7)0.0033 (6)0.0023 (6)0.0081 (6)
C20.0351 (7)0.0496 (9)0.0490 (8)0.0031 (7)0.0048 (6)0.0080 (7)
C30.0422 (9)0.0505 (9)0.0593 (10)0.0019 (7)0.0070 (7)0.0073 (8)
C40.0533 (10)0.0649 (12)0.0645 (12)0.0011 (9)0.0119 (9)0.0174 (9)
C50.0349 (7)0.0487 (8)0.0351 (7)0.0025 (6)0.0041 (6)0.0052 (6)
C60.0652 (11)0.0596 (11)0.0442 (9)0.0058 (9)0.0023 (8)0.0139 (8)
C70.0781 (14)0.0949 (18)0.0380 (9)0.0000 (12)0.0105 (9)0.0129 (10)
C80.0703 (13)0.0866 (16)0.0436 (9)0.0039 (12)0.0036 (9)0.0120 (10)
C90.0686 (12)0.0598 (11)0.0593 (11)0.0067 (10)0.0079 (9)0.0123 (9)
C100.0547 (10)0.0495 (9)0.0448 (8)0.0080 (8)0.0079 (7)0.0001 (7)
C110.0340 (7)0.0454 (8)0.0352 (7)0.0034 (6)0.0002 (6)0.0011 (6)
C120.0478 (9)0.0481 (9)0.0550 (9)0.0091 (7)0.0060 (7)0.0017 (8)
C130.0475 (10)0.0675 (12)0.0669 (12)0.0187 (9)0.0048 (8)0.0095 (10)
C140.0382 (8)0.0880 (14)0.0474 (9)0.0055 (9)0.0064 (7)0.0101 (9)
C150.0404 (8)0.0797 (13)0.0446 (9)0.0077 (9)0.0035 (7)0.0082 (9)
C160.0371 (8)0.0550 (10)0.0468 (8)0.0015 (7)0.0011 (6)0.0085 (7)
C170.0308 (7)0.0353 (7)0.0404 (7)0.0023 (5)0.0011 (5)0.0014 (6)
C180.0525 (9)0.0360 (8)0.0535 (9)0.0028 (7)0.0060 (7)0.0026 (7)
C190.0583 (10)0.0487 (10)0.0579 (10)0.0038 (8)0.0057 (8)0.0175 (8)
C200.0462 (9)0.0618 (11)0.0423 (8)0.0039 (8)0.0026 (7)0.0094 (8)
C210.0359 (7)0.0477 (9)0.0408 (7)0.0057 (6)0.0025 (6)0.0054 (6)
C220.0312 (7)0.0360 (7)0.0409 (7)0.0042 (6)0.0012 (5)0.0026 (6)
C230.0595 (10)0.0372 (8)0.0479 (8)0.0074 (7)0.0002 (7)0.0047 (7)
Geometric parameters (Å, º) top
Cl1—C41.802 (2)C10—H100.9300
Cl2—C211.7491 (17)C11—C161.384 (2)
O1—C31.435 (2)C11—C121.391 (2)
O1—C11.4558 (18)C12—C131.392 (3)
N1—C171.4414 (18)C12—H120.9300
N1—C11.4639 (18)C13—C141.373 (3)
N1—C21.4768 (19)C13—H130.9300
C1—C111.518 (2)C14—C151.374 (3)
C1—C51.539 (2)C14—H140.9300
C2—C31.546 (2)C15—C161.387 (2)
C2—H2A0.9700C15—H150.9300
C2—H2B0.9700C16—H160.9300
C3—C41.503 (3)C17—C181.391 (2)
C3—H30.9800C17—C221.407 (2)
C4—H4A0.9700C18—C191.389 (3)
C4—H4B0.9700C18—H180.9300
C5—C101.386 (2)C19—C201.374 (3)
C5—C61.390 (2)C19—H190.9300
C6—C71.387 (3)C20—C211.382 (3)
C6—H60.9300C20—H200.9300
C7—C81.373 (4)C21—C221.402 (2)
C7—H70.9300C22—C231.501 (2)
C8—C91.378 (3)C23—H23A0.9600
C8—H80.9300C23—H23B0.9600
C9—C101.384 (3)C23—H23C0.9600
C9—H90.9300
C3—O1—C1108.45 (12)C9—C10—H10119.6
C17—N1—C1119.47 (12)C5—C10—H10119.6
C17—N1—C2113.23 (12)C16—C11—C12119.11 (15)
C1—N1—C2102.38 (11)C16—C11—C1119.70 (14)
O1—C1—N1105.77 (12)C12—C11—C1121.02 (14)
O1—C1—C11109.11 (12)C11—C12—C13119.69 (18)
N1—C1—C11115.17 (12)C11—C12—H12120.2
O1—C1—C5109.81 (12)C13—C12—H12120.2
N1—C1—C5109.61 (12)C14—C13—C12120.57 (18)
C11—C1—C5107.32 (12)C14—C13—H13119.7
N1—C2—C3103.81 (12)C12—C13—H13119.7
N1—C2—H2A111.0C13—C14—C15119.96 (17)
C3—C2—H2A111.0C13—C14—H14120.0
N1—C2—H2B111.0C15—C14—H14120.0
C3—C2—H2B111.0C14—C15—C16120.00 (18)
H2A—C2—H2B109.0C14—C15—H15120.0
O1—C3—C4107.96 (15)C16—C15—H15120.0
O1—C3—C2104.71 (13)C11—C16—C15120.67 (17)
C4—C3—C2114.58 (16)C11—C16—H16119.7
O1—C3—H3109.8C15—C16—H16119.7
C4—C3—H3109.8C18—C17—C22120.61 (14)
C2—C3—H3109.8C18—C17—N1123.27 (14)
C3—C4—Cl1109.59 (14)C22—C17—N1116.11 (13)
C3—C4—H4A109.8C19—C18—C17120.32 (16)
Cl1—C4—H4A109.8C19—C18—H18119.8
C3—C4—H4B109.8C17—C18—H18119.8
Cl1—C4—H4B109.8C20—C19—C18120.32 (16)
H4A—C4—H4B108.2C20—C19—H19119.8
C10—C5—C6118.17 (16)C18—C19—H19119.8
C10—C5—C1121.31 (14)C19—C20—C21119.19 (15)
C6—C5—C1120.22 (16)C19—C20—H20120.4
C7—C6—C5120.6 (2)C21—C20—H20120.4
C7—C6—H6119.7C20—C21—C22122.67 (15)
C5—C6—H6119.7C20—C21—Cl2116.88 (12)
C8—C7—C6120.58 (18)C22—C21—Cl2120.45 (13)
C8—C7—H7119.7C21—C22—C17116.89 (14)
C6—C7—H7119.7C21—C22—C23122.73 (14)
C7—C8—C9119.31 (19)C17—C22—C23120.37 (14)
C7—C8—H8120.3C22—C23—H23A109.5
C9—C8—H8120.3C22—C23—H23B109.5
C8—C9—C10120.4 (2)H23A—C23—H23B109.5
C8—C9—H9119.8C22—C23—H23C109.5
C10—C9—H9119.8H23A—C23—H23C109.5
C9—C10—C5120.88 (17)H23B—C23—H23C109.5

Experimental details

Crystal data
Chemical formulaC23H21Cl2NO
Mr398.31
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)25.3638 (9), 7.1591 (2), 22.1688 (7)
β (°) 91.263 (1)
V3)4024.5 (2)
Z8
Radiation typeMo Kα
µ (mm1)0.34
Crystal size (mm)0.53 × 0.48 × 0.39
Data collection
DiffractometerRigaku R-AXIS RAPID
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.834, 0.878
No. of measured, independent and
observed [I > 2σ(I)] reflections
18483, 4564, 3844
Rint0.021
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.131, 1.06
No. of reflections4564
No. of parameters245
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.70, 0.27

Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, CrystalStructure (Rigaku/MSC, 2004), SIR97 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.

 

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