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The crystal structure and absolute configuration of the title compound, C34H33Cl2F3N4O5·CH4O, were determined to examine the validity of van 't Hoff's principle of additivity of optical rotations. The conformation of the dioxolane ring is halfway between an envelope, with the flap at the unsubstituted C atom, and a form twisted about Cmethyl­ene-O. The methanol mol­ecule is hydrogen bonded via the OH group to the unsubstituted N atom of the imidazole group.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805041048/cv6612sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805041048/cv6612Isup2.hkl
Contains datablock I

CCDC reference: 296547

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.009 Å
  • R factor = 0.061
  • wR factor = 0.186
  • Data-to-parameter ratio = 12.9

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 9 PLAT410_ALERT_2_C Short Intra H...H Contact H24 .. H29B .. 1.95 Ang. PLAT410_ALERT_2_C Short Intra H...H Contact H26 .. H33A .. 1.94 Ang.
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 68.92 From the CIF: _reflns_number_total 5861 Count of symmetry unique reflns 3404 Completeness (_total/calc) 172.18% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 2457 Fraction of Friedel pairs measured 0.722 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 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 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Recently we have initiated studies to examine the validity of van 't Hoff's principle of the additivity of optical rotations (van 't Hoff, 1875, 1908). For this purpose we have synthesized the title compound, (I), its epimer and their component halves, namely (2R,4S)-(+)-ketoconazole, (II), (R)-3,3,3-trifluoro-2-methoxy-2-phenyl-1-piperidin-1-yl-propan-1-one and its enantiomer to determine whether the optical rotations of (I) and its epimer can be accounted for as the sum of the individual rotations. In this report we provide the determination of the absolute configuration of (I) needed for the above-described studies on van 't Hoff's principle.

A perspective view of (I) is given in Fig. 1. The bond lengths and angles do not show outstanding features. The molecule contains six rings of which the imidazole and the phenyl rings are essentially planar, with a maximum deviation of 0.014 (8) Å. The conformation of the dioxolane ring is halfway between an envelope with the flap at the unsubstituted C atom and a form twisted about C10—O11. The piperazine ring has a chair conformation, somewhat flattened at N31 due to the sp2 hybridization of that atom. The conformation of (I) (Table 1) is similar to the conformation of (II) in the crystal structure (Peeters et al., 2004). The methanol molecule is hydrogen bonded via the OH group to the unsubstituted N atom of the imidazole group (Table 2). There are no intermolecular contacts that are significantly shorter than the sum of the corresponding van der Waals radii.

Experimental top

The synthesis of (I) was accomplished by first resolving racemic ketoconazole according to a literature method (Redenti et al., 1999) to obtain (+)-ketoconazole, followed by removal of the N-acetyl group of the latter using alkaline hydrolysis according to a published procedure (Chapman et al., 1990). The deacetylated compound was then acetylated with (S)-(+)-α-methoxy-α-trifluoromethylphenylacetyl chloride as described (Hoye & Renner, 1996) to obtain (I). Single crystals were grown by slow evaporation of a methanol solution.

Refinement top

After checking their presence in the difference map, H atoms were inserted at their geometrically calculated positions, except for those of the methyl groups and OH group. The latter were found from a circular difference Fourier synthesis. All H atoms were allowed to ride on their parent atoms, with C—H = 0.93–0.98 Å, O—H = 0.82 Å and Uiso(H) = 1.25–1.50 Ueq of the parent atom.

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: PARST (Nardelli, 1983).

Figures top
[Figure 1] Fig. 1. View of (I), with the atomic numbering scheme and displacement ellipsoids at the 50% probability level.
(+)-1-[(R)-3,3,3-Trifluoro-2-methoxy-2-phenylpropionyl]- 4-(4-{[(2R,4S)-2-(2,4-dichlorophenyl)-2-(1H-imidazol-1-ylmethyl)- 1,3-dioxolan-4-yl]methoxy}phenyl)piperazine methanol solvate top
Crystal data top
C34H33Cl2F3N4O5·CH4OF(000) = 768
Mr = 737.59Dx = 1.391 Mg m3
Monoclinic, P21Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ybCell parameters from 28 reflections
a = 8.389 (1) Åθ = 6.0–27.6°
b = 14.755 (1) ŵ = 2.23 mm1
c = 14.473 (2) ÅT = 293 K
β = 100.47 (1)°Needle, colourless
V = 1761.6 (3) Å30.44 × 0.08 × 0.06 mm
Z = 2
Data collection top
Siemens P4 four-circle
diffractometer
Rint = 0.038
ω/2θ scansθmax = 68.9°
Absorption correction: ψ scan
XEMP (Siemens, 1989)
h = 910
Tmin = 0.560, Tmax = 0.875k = 1717
6518 measured reflectionsl = 1717
5861 independent reflections3 standard reflections every 100 reflections
3978 reflections with F2 > 2σ(F2) intensity decay: none
Refinement top
Refinement on F2 w = 1/[σ2(Fo2) + (0.09P)2 + 0.9675P]
where P = (Fo2 + 2Fc2)/3
Least-squares matrix: full(Δ/σ)max = 0.001
R[F2 > 2σ(F2)] = 0.061Δρmax = 0.28 e Å3
wR(F2) = 0.186Δρmin = 0.31 e Å3
S = 1.07Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin((2θ)]-1/4
5861 reflectionsExtinction coefficient: 0.0119 (9)
455 parametersAbsolute structure: Flack (1983), 2616 Friedel pairs
H-atom parameters constrainedAbsolute structure parameter: 0.01 (2)
Crystal data top
C34H33Cl2F3N4O5·CH4OV = 1761.6 (3) Å3
Mr = 737.59Z = 2
Monoclinic, P21Cu Kα radiation
a = 8.389 (1) ŵ = 2.23 mm1
b = 14.755 (1) ÅT = 293 K
c = 14.473 (2) Å0.44 × 0.08 × 0.06 mm
β = 100.47 (1)°
Data collection top
Siemens P4 four-circle
diffractometer
3978 reflections with F2 > 2σ(F2)
Absorption correction: ψ scan
XEMP (Siemens, 1989)
Rint = 0.038
Tmin = 0.560, Tmax = 0.8753 standard reflections every 100 reflections
6518 measured reflections intensity decay: none
5861 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.061H-atom parameters constrained
wR(F2) = 0.186Δρmax = 0.28 e Å3
S = 1.07Δρmin = 0.31 e Å3
5861 reflectionsAbsolute structure: Flack (1983), 2616 Friedel pairs
455 parametersAbsolute structure parameter: 0.01 (2)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.5288 (6)0.1683 (3)0.4720 (3)0.065 (2)*
C20.6916 (9)0.1631 (4)0.4910 (5)0.078 (3)*
N30.7561 (8)0.1541 (4)0.4164 (5)0.086 (2)*
C40.627 (1)0.1525 (5)0.3442 (6)0.083 (3)*
C50.4852 (9)0.1619 (5)0.3751 (5)0.078 (3)*
C60.4205 (8)0.1821 (4)0.5375 (5)0.069 (2)*
C70.3907 (6)0.2815 (4)0.5580 (4)0.056 (2)*
O80.5387 (5)0.3293 (3)0.5833 (3)0.059 (1)*
C90.5370 (7)0.4074 (4)0.5228 (4)0.063 (2)*
C100.3625 (8)0.4156 (4)0.4772 (5)0.071 (3)*
O110.3095 (5)0.3227 (3)0.4734 (3)0.068 (1)*
C120.2893 (6)0.2867 (4)0.6351 (4)0.054 (2)*
C130.3545 (6)0.2719 (4)0.7293 (4)0.054 (2)*
C140.2588 (7)0.2721 (4)0.7981 (4)0.066 (2)*
C150.0923 (7)0.2859 (4)0.7717 (4)0.067 (2)*
C160.0245 (8)0.2985 (5)0.6788 (5)0.073 (2)*
C170.1240 (7)0.2990 (5)0.6113 (5)0.070 (2)*
Cl180.5589 (2)0.2521 (1)0.7685 (1)0.0699 (5)*
Cl190.0261 (2)0.2848 (2)0.8569 (1)0.0973 (8)*
C200.6491 (8)0.3862 (4)0.4563 (4)0.065 (2)*
O210.6875 (5)0.4669 (3)0.4108 (3)0.066 (1)*
C220.8161 (7)0.4592 (4)0.3628 (4)0.058 (2)*
C230.8715 (8)0.3777 (4)0.3344 (5)0.079 (3)*
C240.9997 (8)0.3747 (4)0.2879 (5)0.075 (3)*
C251.0821 (7)0.4527 (4)0.2697 (4)0.058 (2)*
C261.0245 (7)0.5344 (4)0.2986 (4)0.062 (2)*
C270.8934 (8)0.5373 (4)0.3446 (4)0.065 (2)*
N281.2261 (5)0.4496 (3)0.2308 (3)0.059 (2)*
C291.2513 (8)0.3665 (4)0.1793 (5)0.074 (2)*
C301.4221 (9)0.3619 (5)0.1597 (5)0.081 (3)*
N311.4614 (6)0.4443 (3)0.1116 (3)0.064 (2)*
C321.4380 (8)0.5256 (4)0.1641 (5)0.067 (2)*
C331.2667 (7)0.5305 (4)0.1823 (4)0.063 (2)*
C341.4918 (7)0.4385 (4)0.0235 (4)0.060 (2)*
O351.4900 (6)0.3657 (3)0.0187 (3)0.079 (2)*
C361.5215 (6)0.5263 (4)0.0275 (4)0.054 (2)*
O371.6344 (5)0.5857 (3)0.0274 (3)0.066 (2)*
C381.7827 (8)0.5468 (6)0.0752 (5)0.084 (3)*
C391.3608 (7)0.5772 (4)0.0542 (4)0.057 (2)*
C401.2192 (7)0.5300 (4)0.0892 (5)0.069 (2)*
C411.0737 (8)0.5745 (6)0.1123 (5)0.086 (3)*
C421.066 (1)0.6661 (6)0.0973 (7)0.101 (3)*
C431.204 (1)0.7135 (5)0.0631 (6)0.095 (4)*
C441.3516 (8)0.6704 (4)0.0414 (5)0.069 (2)*
C451.5843 (8)0.5056 (4)0.1180 (5)0.066 (2)*
F461.4769 (5)0.4670 (3)0.1853 (3)0.082 (2)*
F471.6305 (5)0.5830 (3)0.1554 (3)0.089 (2)*
F481.7179 (4)0.4527 (3)0.1049 (3)0.089 (2)*
C491.056 (1)0.0309 (7)0.3656 (7)0.126 (4)*
O501.0745 (7)0.1233 (4)0.3839 (6)0.124 (3)*
H20.75190.16570.55160.097*
H40.63590.14570.28140.104*
H50.38130.16360.33930.097*
H6A0.46520.15210.59610.086*
H6B0.31740.15370.51270.086*
H90.57300.46170.55970.079*
H10A0.30250.45220.51480.089*
H10B0.35130.44160.41480.089*
H140.30500.26320.86080.082*
H160.08680.30670.66100.092*
H170.07750.30790.54860.088*
H20A0.74770.35910.49040.082*
H20B0.59810.34290.40960.082*
H230.82120.32410.34700.099*
H241.03260.31900.26790.094*
H261.07500.58820.28680.078*
H270.85750.59290.36340.081*
H29A1.17470.36490.12040.093*
H29B1.23120.31400.21600.093*
H30A1.49790.35500.21840.101*
H30B1.43260.30940.12080.101*
H32A1.46030.57850.12880.084*
H32B1.51340.52550.22340.084*
H33A1.25540.58350.22020.079*
H33B1.19200.53670.12310.079*
H38A1.75930.49400.10910.126*
H38B1.83970.59030.11830.126*
H38C1.84860.53000.03020.126*
H401.22320.46750.09710.086*
H410.98050.54260.13810.108*
H420.96680.69590.11030.126*
H431.19830.77580.05430.119*
H441.44470.70340.01830.086*
H49A1.13660.01100.33100.189*
H49B0.94990.01970.32940.189*
H49C1.06770.00170.42390.189*
H500.99500.14260.40350.155*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.069 (3)0.060 (3)0.072 (3)0.002 (2)0.025 (3)0.005 (2)
C20.076 (5)0.066 (4)0.092 (5)0.011 (3)0.021 (4)0.002 (3)
N30.078 (4)0.082 (4)0.104 (4)0.003 (3)0.031 (4)0.020 (3)
C40.094 (6)0.071 (4)0.090 (5)0.005 (4)0.031 (5)0.016 (4)
C50.082 (5)0.081 (4)0.071 (4)0.009 (4)0.016 (3)0.015 (3)
C60.083 (4)0.057 (3)0.073 (4)0.003 (3)0.033 (3)0.004 (3)
C70.050 (3)0.053 (3)0.064 (3)0.005 (3)0.013 (3)0.002 (3)
O80.053 (2)0.061 (2)0.064 (2)0.009 (2)0.012 (2)0.006 (2)
C90.070 (4)0.056 (3)0.068 (3)0.002 (3)0.025 (3)0.011 (3)
C100.070 (4)0.065 (4)0.081 (4)0.001 (3)0.016 (3)0.015 (3)
O110.068 (3)0.070 (2)0.064 (2)0.008 (2)0.008 (2)0.009 (2)
C120.045 (3)0.055 (3)0.064 (3)0.001 (2)0.011 (3)0.006 (3)
C130.045 (3)0.055 (3)0.061 (3)0.000 (2)0.013 (2)0.000 (2)
C140.060 (4)0.074 (4)0.065 (3)0.003 (3)0.012 (3)0.002 (3)
C150.051 (3)0.074 (4)0.079 (4)0.003 (3)0.019 (3)0.010 (3)
C160.051 (3)0.077 (4)0.092 (5)0.001 (3)0.014 (3)0.003 (4)
C170.058 (4)0.079 (4)0.073 (4)0.001 (3)0.010 (3)0.005 (3)
Cl180.0557 (8)0.0805 (9)0.0734 (8)0.0098 (7)0.0118 (7)0.0081 (7)
Cl190.074 (1)0.128 (2)0.099 (1)0.002 (1)0.0408 (9)0.008 (1)
C200.069 (4)0.061 (3)0.073 (4)0.005 (3)0.028 (3)0.011 (3)
O210.060 (2)0.061 (2)0.083 (3)0.002 (2)0.033 (2)0.009 (2)
C220.055 (3)0.057 (3)0.065 (3)0.002 (3)0.019 (3)0.002 (3)
C230.079 (5)0.058 (3)0.110 (5)0.015 (3)0.047 (4)0.007 (3)
C240.079 (4)0.056 (3)0.101 (5)0.014 (3)0.044 (4)0.011 (3)
C250.056 (3)0.058 (3)0.062 (3)0.002 (3)0.014 (3)0.002 (3)
C260.056 (4)0.055 (3)0.079 (4)0.001 (3)0.022 (3)0.000 (3)
C270.070 (4)0.053 (3)0.079 (4)0.004 (3)0.030 (3)0.001 (3)
N280.056 (3)0.056 (3)0.067 (3)0.000 (2)0.021 (2)0.002 (2)
C290.084 (5)0.053 (3)0.095 (5)0.002 (3)0.043 (4)0.000 (3)
C300.096 (5)0.066 (4)0.092 (5)0.019 (4)0.046 (4)0.022 (3)
N310.068 (3)0.057 (3)0.073 (3)0.007 (2)0.024 (3)0.006 (2)
C320.064 (4)0.069 (4)0.073 (4)0.003 (3)0.025 (3)0.013 (3)
C330.068 (4)0.050 (3)0.077 (4)0.006 (3)0.027 (3)0.001 (3)
C340.060 (4)0.058 (3)0.065 (3)0.001 (3)0.020 (3)0.001 (3)
O350.098 (3)0.056 (2)0.086 (3)0.010 (2)0.026 (3)0.001 (2)
C360.045 (3)0.060 (3)0.058 (3)0.004 (3)0.010 (3)0.003 (3)
O370.051 (2)0.069 (3)0.075 (2)0.005 (2)0.006 (2)0.002 (2)
C380.046 (4)0.116 (6)0.086 (4)0.007 (4)0.001 (3)0.003 (4)
C390.050 (3)0.055 (3)0.068 (3)0.003 (3)0.014 (3)0.002 (3)
C400.058 (4)0.059 (3)0.086 (4)0.010 (3)0.005 (3)0.002 (3)
C410.047 (4)0.098 (5)0.109 (5)0.011 (4)0.002 (4)0.013 (4)
C420.080 (6)0.090 (5)0.134 (7)0.029 (5)0.022 (5)0.023 (5)
C430.085 (6)0.066 (4)0.136 (7)0.017 (4)0.024 (5)0.010 (4)
C440.066 (4)0.052 (3)0.090 (4)0.002 (3)0.017 (3)0.000 (3)
C450.060 (4)0.069 (4)0.073 (4)0.005 (3)0.022 (3)0.002 (3)
F460.089 (3)0.087 (3)0.072 (2)0.001 (2)0.018 (2)0.012 (2)
F470.101 (3)0.090 (3)0.083 (2)0.015 (2)0.038 (2)0.009 (2)
F480.067 (2)0.104 (3)0.099 (3)0.020 (2)0.028 (2)0.009 (2)
C490.117 (8)0.111 (7)0.139 (8)0.032 (6)0.005 (6)0.024 (6)
O500.073 (4)0.110 (5)0.189 (7)0.009 (3)0.025 (4)0.028 (5)
Geometric parameters (Å, º) top
N1—C21.345 (9)C26—C271.386 (9)
N1—C51.387 (8)C27—H270.930
N1—C61.441 (9)N28—C291.470 (8)
C2—H20.930N28—C331.457 (8)
C2—N31.30 (1)C29—H29A0.970
N3—C41.36 (1)C29—H29B0.970
C4—H40.930C29—C301.51 (1)
C4—C51.36 (1)C30—H30A0.970
C5—H50.930C30—H30B0.970
C6—H6A0.970C30—N311.468 (9)
C6—H6B0.970N31—C321.451 (8)
C6—C71.526 (8)N31—C341.349 (8)
C7—O81.416 (6)C32—H32A0.970
C7—O111.425 (6)C32—H32B0.970
C7—C121.523 (8)C32—C331.509 (9)
O8—C91.446 (7)C33—H33A0.970
C9—H90.980C33—H33B0.970
C9—C101.497 (8)C34—O351.234 (7)
C9—C201.50 (1)C34—C361.534 (8)
C10—H10A0.970C36—O371.423 (6)
C10—H10B0.970C36—C391.530 (8)
C10—O111.439 (8)C36—C451.529 (9)
C12—C131.391 (7)O37—C381.429 (7)
C12—C171.379 (8)C38—H38A0.960
C13—C141.388 (9)C38—H38B0.960
C13—Cl181.730 (5)C38—H38C0.960
C14—H140.930C39—C401.391 (8)
C14—C151.394 (8)C39—C441.391 (8)
C15—C161.375 (9)C40—H400.930
C15—Cl191.717 (7)C40—C411.373 (9)
C16—H160.930C41—H410.930
C16—C171.40 (1)C41—C421.37 (1)
C17—H170.930C42—H420.930
C20—H20A0.970C42—C431.37 (1)
C20—H20B0.970C43—H430.930
C20—O211.426 (7)C43—C441.38 (1)
O21—C221.389 (7)C44—H440.930
C22—C231.378 (9)C45—F461.329 (7)
C22—C271.372 (8)C45—F471.350 (8)
C23—H230.930C45—F481.351 (7)
C23—C241.37 (1)C49—H49A0.960
C24—H240.930C49—H49B0.960
C24—C251.392 (9)C49—H49C0.960
C25—C261.391 (8)C49—O501.39 (1)
C25—N281.424 (8)O50—H500.820
C26—H260.930
C2—N1—C5105.9 (6)C22—C27—H27119.7
C2—N1—C6127.6 (6)C26—C27—H27119.7
C5—N1—C6126.4 (5)C25—N28—C29116.0 (5)
N1—C2—H2123.3C25—N28—C33117.0 (4)
N1—C2—N3113.4 (6)C29—N28—C33111.8 (4)
H2—C2—N3123.3N28—C29—H29A109.4
C2—N3—C4104.3 (7)N28—C29—H29B109.4
N3—C4—H4124.2N28—C29—C30111.2 (5)
N3—C4—C5111.6 (7)H29A—C29—H29B108.0
H4—C4—C5124.2H29A—C29—C30109.4
N1—C5—C4104.8 (6)H29B—C29—C30109.4
N1—C5—H5127.6C29—C30—H30A109.5
C4—C5—H5127.6C29—C30—H30B109.5
N1—C6—H6A108.7C29—C30—N31110.8 (6)
N1—C6—H6B108.7H30A—C30—H30B108.1
N1—C6—C7114.1 (5)H30A—C30—N31109.5
H6A—C6—H6B107.7H30B—C30—N31109.5
H6A—C6—C7108.7C30—N31—C32111.9 (5)
H6B—C6—C7108.7C30—N31—C34119.6 (5)
C6—C7—O8111.2 (4)C32—N31—C34127.9 (5)
C6—C7—O11108.3 (4)N31—C32—H32A109.5
C6—C7—C12108.8 (5)N31—C32—H32B109.5
O8—C7—O11105.7 (4)N31—C32—C33110.8 (5)
O8—C7—C12111.4 (4)H32A—C32—H32B108.1
O11—C7—C12111.4 (4)H32A—C32—C33109.5
C7—O8—C9109.1 (4)H32B—C32—C33109.5
O8—C9—H9110.7N28—C33—C32111.0 (5)
O8—C9—C10103.5 (5)N28—C33—H33A109.4
O8—C9—C20106.6 (5)N28—C33—H33B109.4
H9—C9—C10110.7C32—C33—H33A109.4
H9—C9—C20110.7C32—C33—H33B109.4
C10—C9—C20114.3 (5)H33A—C33—H33B108.0
C9—C10—H10A111.3N31—C34—O35122.4 (5)
C9—C10—H10B111.3N31—C34—C36118.5 (5)
C9—C10—O11102.2 (5)O35—C34—C36119.1 (5)
H10A—C10—H10B109.2C34—C36—O37113.7 (4)
H10A—C10—O11111.3C34—C36—C39108.8 (4)
H10B—C10—O11111.3C34—C36—C45110.8 (5)
C7—O11—C10106.1 (4)O37—C36—C39107.8 (4)
C7—C12—C13122.5 (5)O37—C36—C45107.7 (4)
C7—C12—C17119.6 (5)C39—C36—C45107.9 (5)
C13—C12—C17117.6 (5)C36—O37—C38117.1 (4)
C12—C13—C14121.8 (5)O37—C38—H38A109.5
C12—C13—Cl18122.6 (4)O37—C38—H38B109.5
C14—C13—Cl18115.6 (4)O37—C38—H38C109.5
C13—C14—H14120.5H38A—C38—H38B109.5
C13—C14—C15119.0 (5)H38A—C38—H38C109.5
H14—C14—C15120.5H38B—C38—H38C109.5
C14—C15—C16120.2 (6)C36—C39—C40120.1 (5)
C14—C15—Cl19118.9 (5)C36—C39—C44121.3 (5)
C16—C15—Cl19120.8 (5)C40—C39—C44118.6 (5)
C15—C16—H16120.3C39—C40—H40119.6
C15—C16—C17119.5 (6)C39—C40—C41120.8 (6)
H16—C16—C17120.3H40—C40—C41119.6
C12—C17—C16121.8 (6)C40—C41—H41120.1
C12—C17—H17119.1C40—C41—C42119.8 (7)
C16—C17—H17119.1H41—C41—C42120.1
C9—C20—H20A109.6C41—C42—H42120.0
C9—C20—H20B109.6C41—C42—C43120.0 (8)
C9—C20—O21110.1 (5)H42—C42—C43120.0
H20A—C20—H20B108.2C42—C43—H43119.6
H20A—C20—O21109.6C42—C43—C44120.9 (8)
H20B—C20—O21109.6H43—C43—C44119.6
C20—O21—C22115.0 (4)C39—C44—C43119.8 (6)
O21—C22—C23123.8 (5)C39—C44—H44120.1
O21—C22—C27117.6 (5)C43—C44—H44120.1
C23—C22—C27118.6 (5)C36—C45—F46114.8 (5)
C22—C23—H23119.6C36—C45—F47110.1 (5)
C22—C23—C24120.8 (6)C36—C45—F48113.6 (5)
H23—C23—C24119.6F46—C45—F47106.0 (5)
C23—C24—H24119.1F46—C45—F48106.9 (5)
C23—C24—C25121.9 (6)F47—C45—F48104.7 (5)
H24—C24—C25119.1H49A—C49—H49B109.5
C24—C25—C26116.6 (5)H49A—C49—H49C109.5
C24—C25—N28122.3 (5)H49A—C49—O50109.5
C26—C25—N28120.9 (5)H49B—C49—H49C109.5
C25—C26—H26119.3H49B—C49—O50109.5
C25—C26—C27121.4 (5)H49C—C49—O50109.5
H26—C26—C27119.3C49—O50—H50109.5
C22—C27—C26120.7 (6)
C5—N1—C2—H2180.0C24—C25—C26—H26178.9
C5—N1—C2—N30.0 (8)C24—C25—C26—C271.1 (9)
C6—N1—C2—H22.8N28—C25—C26—H266.2
C6—N1—C2—N3177.2 (6)N28—C25—C26—C27173.9 (5)
C2—N1—C5—C40.5 (8)C24—C25—N28—C2921.7 (8)
C2—N1—C5—H5179.5C24—C25—N28—C33157.2 (6)
C6—N1—C5—C4177.8 (6)C26—C25—N28—C29163.6 (5)
C6—N1—C5—H52.2C26—C25—N28—C3328.2 (8)
C2—N1—C6—H6A34.6C25—C26—C27—C220.2 (9)
C2—N1—C6—H6B151.5C25—C26—C27—H27179.8
C2—N1—C6—C787.0 (8)H26—C26—C27—C22179.8
C5—N1—C6—H6A148.7H26—C26—C27—H270.2
C5—N1—C6—H6B31.8C25—N28—C29—H29A71.4
C5—N1—C6—C789.8 (7)C25—N28—C29—H29B46.7
N1—C2—N3—C40.6 (8)C25—N28—C29—C30167.7 (5)
H2—C2—N3—C4179.4C33—N28—C29—H29A66.3
C2—N3—C4—H4179.1C33—N28—C29—H29B175.6
C2—N3—C4—C50.9 (9)C33—N28—C29—C3054.7 (7)
N3—C4—C5—N10.9 (8)C25—N28—C33—C32167.3 (5)
N3—C4—C5—H5179.1C25—N28—C33—H33A46.4
H4—C4—C5—N1179.1C25—N28—C33—H33B71.8
H4—C4—C5—H50.9C29—N28—C33—C3255.4 (6)
N1—C6—C7—O851.1 (6)C29—N28—C33—H33A176.3
N1—C6—C7—O1164.5 (6)C29—N28—C33—H33B65.5
N1—C6—C7—C12174.3 (5)N28—C29—C30—H30A66.9
H6A—C6—C7—O870.4N28—C29—C30—H30B174.8
H6A—C6—C7—O11174.0N28—C29—C30—N3154.0 (7)
H6A—C6—C7—C1252.7H29A—C29—C30—H30A172.2
H6B—C6—C7—O8172.7H29A—C29—C30—H30B53.9
H6B—C6—C7—O1157.0H29A—C29—C30—N3167.0
H6B—C6—C7—C1264.2H29B—C29—C30—H30A54.0
C6—C7—O8—C9125.7 (5)H29B—C29—C30—H30B64.3
O11—C7—O8—C98.4 (5)H29B—C29—C30—N31174.9
C12—C7—O8—C9112.7 (5)C29—C30—N31—C3255.6 (7)
C6—C7—O11—C10148.3 (5)C29—C30—N31—C34115.8 (6)
O8—C7—O11—C1029.0 (5)H30A—C30—N31—C3265.2
C12—C7—O11—C1092.1 (5)H30A—C30—N31—C34123.4
C6—C7—C12—C1376.7 (6)H30B—C30—N31—C32176.4
C6—C7—C12—C1797.8 (6)H30B—C30—N31—C345.0
O8—C7—C12—C1346.3 (7)C30—N31—C32—H32A177.4
O8—C7—C12—C17139.2 (5)C30—N31—C32—H32B64.3
O11—C7—C12—C13164.0 (5)C30—N31—C32—C3356.5 (7)
O11—C7—C12—C1721.5 (7)C34—N31—C32—H32A6.9
C7—O8—C9—H9132.9C34—N31—C32—H32B125.1
C7—O8—C9—C1014.2 (6)C34—N31—C32—C33114.0 (6)
C7—O8—C9—C20106.7 (5)C30—N31—C34—O351.0 (9)
O8—C9—C10—H10A88.0C30—N31—C34—C36176.0 (5)
O8—C9—C10—H10B149.9C32—N31—C34—O35170.9 (6)
O8—C9—C10—O1131.0 (6)C32—N31—C34—C366.2 (9)
H9—C9—C10—H10A30.6N31—C32—C33—N2856.1 (6)
H9—C9—C10—H10B91.5N31—C32—C33—H33A177.0
H9—C9—C10—O11149.6N31—C32—C33—H33B64.8
C20—C9—C10—H10A156.5H32A—C32—C33—N28176.9
C20—C9—C10—H10B34.4H32A—C32—C33—H33A62.2
C20—C9—C10—O1184.5 (6)H32A—C32—C33—H33B56.0
O8—C9—C20—H20A44.2H32B—C32—C33—N2864.8
O8—C9—C20—H20B74.4H32B—C32—C33—H33A56.1
O8—C9—C20—O21164.9 (4)H32B—C32—C33—H33B174.3
H9—C9—C20—H20A76.3N31—C34—C36—O3748.0 (7)
H9—C9—C20—H20B165.2N31—C34—C36—C3972.1 (6)
H9—C9—C20—O2144.5N31—C34—C36—C45169.4 (5)
C10—C9—C20—H20A157.9O35—C34—C36—O37134.9 (5)
C10—C9—C20—H20B39.3O35—C34—C36—C39105.0 (6)
C10—C9—C20—O2181.4 (6)O35—C34—C36—C4513.4 (7)
C9—C10—O11—C737.2 (6)C34—C36—O37—C3847.4 (6)
H10A—C10—O11—C781.7C39—C36—O37—C38168.1 (5)
H10B—C10—O11—C7156.2C45—C36—O37—C3875.8 (6)
C7—C12—C13—C14176.6 (5)C34—C36—C39—C4041.6 (7)
C7—C12—C13—Cl183.5 (7)C34—C36—C39—C44136.4 (6)
C17—C12—C13—C142.0 (8)O37—C36—C39—C40165.4 (5)
C17—C12—C13—Cl18178.1 (4)O37—C36—C39—C4412.6 (7)
C7—C12—C17—C16175.9 (6)C45—C36—C39—C4078.7 (6)
C7—C12—C17—H174.1C45—C36—C39—C44103.3 (6)
C13—C12—C17—C161.2 (9)C34—C36—C45—F4668.8 (6)
C13—C12—C17—H17178.8C34—C36—C45—F47171.8 (5)
C12—C13—C14—H14178.8C34—C36—C45—F4854.7 (7)
C12—C13—C14—C151.2 (9)O37—C36—C45—F46166.3 (5)
Cl18—C13—C14—H141.2O37—C36—C45—F4746.9 (6)
Cl18—C13—C14—C15178.8 (5)O37—C36—C45—F4870.2 (6)
C13—C14—C15—C160.3 (9)C39—C36—C45—F4650.3 (6)
C13—C14—C15—Cl19179.2 (4)C39—C36—C45—F4769.2 (6)
H14—C14—C15—C16179.7C39—C36—C45—F48173.7 (5)
H14—C14—C15—Cl190.8C36—O37—C38—H38A49.7
C14—C15—C16—H16178.9C36—O37—C38—H38B169.6
C14—C15—C16—C171 (1)C36—O37—C38—H38C70.4
Cl19—C15—C16—H160.1C36—C39—C40—H400.8
Cl19—C15—C16—C17179.9 (5)C36—C39—C40—C41179.2 (6)
C15—C16—C17—C120 (1)C44—C39—C40—H40178.9
C15—C16—C17—H17179.7C44—C39—C40—C411.1 (9)
H16—C16—C17—C12179.7C36—C39—C44—C43177.8 (6)
H16—C16—C17—H170.3C36—C39—C44—H442.2
C9—C20—O21—C22167.0 (5)C40—C39—C44—C430.3 (9)
H20A—C20—O21—C2246.3C40—C39—C44—H44179.7
H20B—C20—O21—C2272.3C39—C40—C41—H41177.3
C20—O21—C22—C2319.8 (8)C39—C40—C41—C422 (1)
C20—O21—C22—C27158.9 (5)H40—C40—C41—H412.7
O21—C22—C23—H230.5H40—C40—C41—C42177.4
O21—C22—C23—C24179.5 (6)C40—C41—C42—H42177.2
C27—C22—C23—H23179.2C40—C41—C42—C433 (1)
C27—C22—C23—C240 (1)H41—C41—C42—H422.8
O21—C22—C27—C26178.8 (5)H41—C41—C42—C43177.2
O21—C22—C27—H271.2C41—C42—C43—H43178.6
C23—C22—C27—C260.0 (9)C41—C42—C43—C440 (1)
C23—C22—C27—H27180.0H42—C42—C43—H431.4
C22—C23—C24—H24178.1H42—C42—C43—C44178.6
C22—C23—C24—C252 (1)C42—C43—C44—C390 (1)
H23—C23—C24—H241.9C42—C43—C44—H44179.9
H23—C23—C24—C25178.1H43—C43—C44—C39179.9
C23—C24—C25—C261.9 (9)H43—C43—C44—H440.1
C23—C24—C25—N28172.9 (6)H49A—C49—O50—H50168.2
H24—C24—C25—C26178.1H49B—C49—O50—H5048.2
H24—C24—C25—N287.1H49C—C49—O50—H5071.8
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O50—H50···N30.822.052.832 (9)158

Experimental details

Crystal data
Chemical formulaC34H33Cl2F3N4O5·CH4O
Mr737.59
Crystal system, space groupMonoclinic, P21
Temperature (K)293
a, b, c (Å)8.389 (1), 14.755 (1), 14.473 (2)
β (°) 100.47 (1)
V3)1761.6 (3)
Z2
Radiation typeCu Kα
µ (mm1)2.23
Crystal size (mm)0.44 × 0.08 × 0.06
Data collection
DiffractometerSiemens P4 four-circle
diffractometer
Absorption correctionψ scan
XEMP (Siemens, 1989)
Tmin, Tmax0.560, 0.875
No. of measured, independent and
observed [F2 > 2σ(F2)] reflections
6518, 5861, 3978
Rint0.038
(sin θ/λ)max1)0.605
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.061, 0.186, 1.07
No. of reflections5861
No. of parameters455
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.28, 0.31
Absolute structureFlack (1983), 2616 Friedel pairs
Absolute structure parameter0.01 (2)

Computer programs: XSCANS (Siemens, 1996), XSCANS, SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), DIAMOND (Bergerhoff, 1996), PARST (Nardelli, 1983).

Selected torsion angles (º) top
C2—N1—C6—C787.0 (8)C9—C20—O21—C22167.0 (5)
N1—C6—C7—O851.1 (6)C20—O21—C22—C2319.8 (8)
N1—C6—C7—O1164.5 (6)C23—C24—C25—N28172.9 (6)
N1—C6—C7—C12174.3 (5)C24—C25—N28—C2921.7 (8)
C6—C7—O8—C9125.7 (5)C25—N28—C29—C30167.7 (5)
O11—C7—O8—C98.4 (5)C29—C30—N31—C34115.8 (6)
O8—C7—O11—C1029.0 (5)C30—N31—C34—C36176.0 (5)
C6—C7—C12—C1376.7 (6)N31—C34—C36—O3748.0 (7)
C7—O8—C9—C1014.2 (6)N31—C34—C36—C3972.1 (6)
C7—O8—C9—C20106.7 (5)N31—C34—C36—C45169.4 (5)
O8—C9—C10—O1131.0 (6)O35—C34—C36—O37134.9 (5)
O8—C9—C20—O21164.9 (4)C34—C36—C39—C4041.6 (7)
C9—C10—O11—C737.2 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O50—H50···N30.822.052.832 (9)158
 

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