Literature DB >> 21580078

2,4-Bis(2-fluoro-phen-yl)-1-methyl-3-aza-bicyclo-[3.3.1]nonan-9-one.

P Parthiban, V Ramkumar, Yeon Tae Jeong.   

Abstract

The crystal structure of the title compound, C(21)H(21)F(2)NO, shows that the compound exists in a twin-chair conformation with an equatorial orientation of the ortho-fluoro-phenyl groups on either side of the secondary amino group. The title compound is a 1-methyl-ated analog of 2,4-bis-(2-fluoro-phen-yl)-3-aza-bicyclo-[3.3.1]nonan-9-one; the two compound both exhibit the same stereochemistry but the orientation of the ortho-fluoro-phenyl rings differs slightly. In the title compound, the rings are orientated at a dihedral angle of 36.70 (3)° with respect to one another, whereas in the non-methyl analog, the angle is 25.68 (4)°. The crystal structure of the title compound is stabilized by an inter-molecular N-H⋯π inter-action and a weak C-H⋯F inter-action.

Entities:  

Year:  2009        PMID： 21580078      PMCID： PMC2980085          DOI： 10.1107/S1600536809053677

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For the synthesis and biological activities of 3-aza­bicyclo­[3.3.1]nonan-9-ones, see: Parthiban, Aridoss et al. (2009 ▶); Hardick et al. (1996 ▶); Jeyaraman & Avila (1981 ▶). For the structure of the non-methyl­ated analog of the title compound, see: Parthiban Ramkumar & Jeong (2009 ▶). For puckering and asymmetry parameters, see: Cremer & Pople (1975 ▶); Nardelli (1983 ▶).

Experimental

Crystal data

C21H21F2NO M = 341.39 Triclinic, a = 7.8481 (3) Å b = 10.5417 (4) Å c = 10.9333 (4) Å α = 76.196 (2)° β = 80.026 (2)° γ = 86.014 (2)° V = 864.76 (6) Å3 Z = 2 Mo Kα radiation μ = 0.10 mm−1 T = 298 K 0.25 × 0.22 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T min = 0.977, T max = 0.986 11190 measured reflections 3936 independent reflections 2176 reflections with I > 2σ(I) R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.054 wR(F 2) = 0.187 S = 0.91 3936 reflections 231 parameters H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.16 e Å−3 Δρmin = −0.19 e Å−3 Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97. Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809053677/zl2256sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536809053677/zl2256Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
C21H21F2NOZ = 2
Mr = 341.39F(000) = 360
Triclinic, P1Dx = 1.311 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.8481 (3) ÅCell parameters from 2446 reflections
b = 10.5417 (4) Åθ = 2.4–22.5°
c = 10.9333 (4) ŵ = 0.10 mm−1
α = 76.196 (2)°T = 298 K
β = 80.026 (2)°Block, colourless
γ = 86.014 (2)°0.25 × 0.22 × 0.15 mm
V = 864.76 (6) Å3
Bruker APEXII CCD area-detector diffractometer3936 independent reflections
Radiation source: fine-focus sealed tube2176 reflections with I > 2σ(I)
graphiteRint = 0.029
phi and ω scansθmax = 28.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 1999)h = −10→10
Tmin = 0.977, Tmax = 0.986k = −13→13
11190 measured reflectionsl = −14→14
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.187H atoms treated by a mixture of independent and constrained refinement
S = 0.91w = 1/[σ2(Fo2) + (0.1P)2 + 0.2445P] where P = (Fo2 + 2Fc2)/3
3936 reflections(Δ/σ)max < 0.001
231 parametersΔρmax = 0.16 e Å−3
0 restraintsΔρmin = −0.19 e Å−3
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.
xyzUiso*/Ueq
C10.2444 (4)0.5969 (3)0.5055 (3)0.0676 (8)
H1A0.17720.53680.47990.081*
H1B0.34680.61680.44120.081*
C20.1369 (3)0.7231 (3)0.5091 (2)0.0583 (7)
H20.08990.75150.42910.070*
C30.2341 (3)0.8380 (2)0.52767 (19)0.0452 (5)
H30.15340.91320.52790.054*
C40.1498 (3)0.7686 (2)0.75818 (19)0.0436 (5)
H40.07070.84510.75350.052*
C50.0465 (3)0.6521 (2)0.7466 (2)0.0501 (6)
C60.1566 (3)0.5251 (2)0.7448 (3)0.0600 (7)
H6A0.20770.50130.82220.072*
H6B0.07990.45590.74730.072*
C70.3003 (4)0.5299 (3)0.6319 (3)0.0668 (7)
H7A0.34050.44150.62890.080*
H7B0.39660.57600.64400.080*
C8−0.0112 (3)0.6929 (3)0.6171 (2)0.0584 (7)
C90.3833 (3)0.8758 (2)0.41980 (19)0.0447 (5)
C100.3558 (4)0.9528 (2)0.3033 (2)0.0565 (6)
C110.4824 (5)0.9830 (3)0.1988 (2)0.0733 (8)
H110.45701.03510.12230.088*
C120.6469 (5)0.9350 (3)0.2091 (3)0.0748 (9)
H120.73460.95250.13880.090*
C130.6817 (4)0.8612 (3)0.3235 (3)0.0701 (8)
H130.79410.83020.33110.084*
C140.5517 (3)0.8322 (2)0.4280 (2)0.0534 (6)
H140.57830.78230.50510.064*
C150.2188 (3)0.7452 (2)0.88251 (19)0.0437 (5)
C160.3783 (3)0.6841 (2)0.8993 (2)0.0514 (6)
H160.44540.65480.83210.062*
C170.4399 (4)0.6658 (3)1.0139 (2)0.0640 (7)
H170.54670.62391.02320.077*
C180.3426 (5)0.7099 (3)1.1141 (2)0.0751 (9)
H180.38370.69751.19110.090*
C190.1865 (4)0.7716 (3)1.1004 (2)0.0756 (9)
H190.12050.80221.16720.091*
C200.1285 (3)0.7877 (3)0.9871 (2)0.0590 (7)
C26−0.1093 (3)0.6268 (3)0.8521 (3)0.0708 (8)
H26A−0.17760.70610.85120.106*
H26B−0.07060.59730.93310.106*
H26C−0.17800.56100.83870.106*
F10.1900 (2)0.99679 (17)0.29190 (15)0.0867 (6)
F2−0.0261 (2)0.85258 (19)0.97406 (16)0.0886 (6)
N10.2938 (2)0.80018 (18)0.65115 (15)0.0414 (4)
O1−0.1609 (2)0.6966 (2)0.6023 (2)0.0911 (7)
H10.352 (3)0.868 (2)0.661 (2)0.061 (7)*
U11U22U33U12U13U23
C10.0685 (18)0.0717 (18)0.0706 (17)−0.0167 (14)0.0039 (14)−0.0388 (14)
C20.0515 (15)0.0824 (18)0.0473 (13)−0.0085 (13)−0.0141 (11)−0.0209 (12)
C30.0426 (13)0.0513 (14)0.0408 (11)0.0064 (10)−0.0075 (9)−0.0106 (9)
C40.0388 (12)0.0488 (13)0.0413 (11)0.0047 (10)−0.0027 (9)−0.0113 (9)
C50.0357 (12)0.0569 (15)0.0564 (13)−0.0060 (10)−0.0016 (10)−0.0134 (11)
C60.0565 (16)0.0509 (15)0.0720 (16)−0.0102 (12)−0.0044 (12)−0.0149 (12)
C70.0633 (17)0.0474 (15)0.091 (2)−0.0003 (12)0.0027 (15)−0.0300 (13)
C80.0416 (14)0.0707 (17)0.0678 (16)−0.0074 (12)−0.0144 (12)−0.0196 (13)
C90.0522 (14)0.0410 (12)0.0414 (11)0.0013 (10)−0.0063 (10)−0.0118 (9)
C100.0731 (18)0.0460 (14)0.0500 (14)0.0025 (12)−0.0139 (12)−0.0091 (11)
C110.118 (3)0.0537 (17)0.0451 (14)−0.0168 (17)−0.0047 (15)−0.0065 (11)
C120.094 (2)0.0601 (18)0.0645 (18)−0.0223 (16)0.0210 (16)−0.0207 (14)
C130.0612 (18)0.0632 (17)0.0778 (19)−0.0068 (13)0.0133 (14)−0.0164 (14)
C140.0507 (15)0.0532 (14)0.0514 (13)−0.0013 (11)−0.0020 (11)−0.0073 (10)
C150.0450 (13)0.0445 (13)0.0392 (11)−0.0065 (10)0.0008 (9)−0.0092 (9)
C160.0540 (15)0.0527 (14)0.0463 (12)−0.0029 (11)−0.0064 (10)−0.0098 (10)
C170.0689 (18)0.0700 (17)0.0522 (14)−0.0101 (14)−0.0164 (13)−0.0054 (12)
C180.100 (2)0.083 (2)0.0456 (14)−0.0274 (18)−0.0164 (15)−0.0100 (13)
C190.091 (2)0.092 (2)0.0472 (15)−0.0159 (18)0.0052 (14)−0.0301 (14)
C200.0582 (16)0.0668 (17)0.0522 (14)−0.0039 (13)0.0036 (11)−0.0221 (12)
C260.0518 (16)0.088 (2)0.0667 (17)−0.0164 (14)0.0069 (13)−0.0139 (14)
F10.0946 (13)0.0890 (12)0.0711 (10)0.0197 (10)−0.0347 (9)0.0008 (8)
F20.0749 (12)0.1137 (14)0.0816 (12)0.0195 (10)0.0047 (9)−0.0502 (10)
N10.0409 (10)0.0458 (11)0.0380 (9)−0.0043 (8)−0.0051 (7)−0.0107 (8)
O10.0441 (12)0.138 (2)0.0938 (15)−0.0129 (11)−0.0233 (10)−0.0196 (13)
C1—C71.518 (4)C10—F11.366 (3)
C1—C21.530 (4)C10—C111.368 (4)
C1—H1A0.9700C11—C121.367 (4)
C1—H1B0.9700C11—H110.9300
C2—C81.498 (3)C12—C131.367 (4)
C2—C31.546 (3)C12—H120.9300
C2—H20.9800C13—C141.383 (3)
C3—N11.462 (3)C13—H130.9300
C3—C91.511 (3)C14—H140.9300
C3—H30.9800C15—C161.388 (3)
C4—N11.472 (3)C15—C201.390 (3)
C4—C151.510 (3)C16—C171.386 (3)
C4—C51.558 (3)C16—H160.9300
C4—H40.9800C17—C181.380 (4)
C5—C81.517 (3)C17—H170.9300
C5—C261.519 (3)C18—C191.361 (4)
C5—C61.545 (3)C18—H180.9300
C6—C71.515 (3)C19—C201.361 (4)
C6—H6A0.9700C19—H190.9300
C6—H6B0.9700C20—F21.363 (3)
C7—H7A0.9700C26—H26A0.9600
C7—H7B0.9700C26—H26B0.9600
C8—O11.210 (3)C26—H26C0.9600
C9—C141.380 (3)N1—H10.91 (3)
C9—C101.380 (3)
C7—C1—C2113.9 (2)C14—C9—C10115.8 (2)
C7—C1—H1A108.8C14—C9—C3123.27 (19)
C2—C1—H1A108.8C10—C9—C3120.9 (2)
C7—C1—H1B108.8F1—C10—C11118.8 (2)
C2—C1—H1B108.8F1—C10—C9117.2 (2)
H1A—C1—H1B107.7C11—C10—C9124.0 (3)
C8—C2—C1108.0 (2)C12—C11—C10118.7 (3)
C8—C2—C3107.75 (19)C12—C11—H11120.7
C1—C2—C3115.7 (2)C10—C11—H11120.7
C8—C2—H2108.4C13—C12—C11119.5 (3)
C1—C2—H2108.4C13—C12—H12120.2
C3—C2—H2108.4C11—C12—H12120.2
N1—C3—C9111.31 (17)C12—C13—C14120.8 (3)
N1—C3—C2108.96 (18)C12—C13—H13119.6
C9—C3—C2110.57 (18)C14—C13—H13119.6
N1—C3—H3108.6C9—C14—C13121.2 (2)
C9—C3—H3108.6C9—C14—H14119.4
C2—C3—H3108.6C13—C14—H14119.4
N1—C4—C15109.29 (17)C16—C15—C20115.3 (2)
N1—C4—C5110.94 (17)C16—C15—C4122.74 (18)
C15—C4—C5113.42 (18)C20—C15—C4121.9 (2)
N1—C4—H4107.7C17—C16—C15121.6 (2)
C15—C4—H4107.7C17—C16—H16119.2
C5—C4—H4107.7C15—C16—H16119.2
C8—C5—C26110.4 (2)C18—C17—C16120.0 (3)
C8—C5—C6105.7 (2)C18—C17—H17120.0
C26—C5—C6110.3 (2)C16—C17—H17120.0
C8—C5—C4105.82 (18)C19—C18—C17120.0 (2)
C26—C5—C4110.4 (2)C19—C18—H18120.0
C6—C5—C4113.98 (18)C17—C18—H18120.0
C7—C6—C5116.2 (2)C20—C19—C18118.9 (2)
C7—C6—H6A108.2C20—C19—H19120.5
C5—C6—H6A108.2C18—C19—H19120.5
C7—C6—H6B108.2C19—C20—F2118.1 (2)
C5—C6—H6B108.2C19—C20—C15124.2 (3)
H6A—C6—H6B107.4F2—C20—C15117.7 (2)
C6—C7—C1113.1 (2)C5—C26—H26A109.5
C6—C7—H7A109.0C5—C26—H26B109.5
C1—C7—H7A109.0H26A—C26—H26B109.5
C6—C7—H7B109.0C5—C26—H26C109.5
C1—C7—H7B109.0H26A—C26—H26C109.5
H7A—C7—H7B107.8H26B—C26—H26C109.5
O1—C8—C2123.5 (2)C3—N1—C4112.26 (16)
O1—C8—C5123.5 (2)C3—N1—H1108.6 (15)
C2—C8—C5112.95 (19)C4—N1—H1108.9 (15)
C7—C1—C2—C8−53.1 (3)C14—C9—C10—F1179.6 (2)
C7—C1—C2—C367.6 (3)C3—C9—C10—F12.5 (3)
C8—C2—C3—N158.7 (2)C14—C9—C10—C112.0 (4)
C1—C2—C3—N1−62.2 (2)C3—C9—C10—C11−175.1 (2)
C8—C2—C3—C9−178.63 (19)F1—C10—C11—C12−177.7 (2)
C1—C2—C3—C960.5 (3)C9—C10—C11—C12−0.2 (4)
N1—C4—C5—C8−56.4 (2)C10—C11—C12—C13−1.6 (4)
C15—C4—C5—C8−179.84 (18)C11—C12—C13—C141.4 (4)
N1—C4—C5—C26−175.92 (19)C10—C9—C14—C13−2.1 (3)
C15—C4—C5—C2660.6 (3)C3—C9—C14—C13174.9 (2)
N1—C4—C5—C659.3 (2)C12—C13—C14—C90.5 (4)
C15—C4—C5—C6−64.2 (2)N1—C4—C15—C16−36.4 (3)
C8—C5—C6—C751.3 (3)C5—C4—C15—C1688.0 (2)
C26—C5—C6—C7170.7 (2)N1—C4—C15—C20141.4 (2)
C4—C5—C6—C7−64.5 (3)C5—C4—C15—C20−94.2 (3)
C5—C6—C7—C1−44.2 (3)C20—C15—C16—C171.0 (3)
C2—C1—C7—C644.0 (3)C4—C15—C16—C17178.9 (2)
C1—C2—C8—O1−113.1 (3)C15—C16—C17—C18−0.6 (4)
C3—C2—C8—O1121.3 (3)C16—C17—C18—C19−0.1 (4)
C1—C2—C8—C564.7 (3)C17—C18—C19—C200.5 (4)
C3—C2—C8—C5−60.9 (3)C18—C19—C20—F2−178.4 (2)
C26—C5—C8—O1−3.9 (4)C18—C19—C20—C15−0.1 (4)
C6—C5—C8—O1115.4 (3)C16—C15—C20—C19−0.6 (4)
C4—C5—C8—O1−123.4 (3)C4—C15—C20—C19−178.6 (2)
C26—C5—C8—C2178.3 (2)C16—C15—C20—F2177.7 (2)
C6—C5—C8—C2−62.4 (3)C4—C15—C20—F2−0.3 (3)
C4—C5—C8—C258.8 (3)C9—C3—N1—C4177.41 (17)
N1—C3—C9—C1424.1 (3)C2—C3—N1—C4−60.4 (2)
C2—C3—C9—C14−97.1 (2)C15—C4—N1—C3−173.77 (18)
N1—C3—C9—C10−159.0 (2)C5—C4—N1—C360.4 (2)
C2—C3—C9—C1079.7 (3)
Cg1 is the centroid of the C9–C14 ring.
D—H···AD—HH···AD···AD—H···A
N1—H1···Cg1i0.911 (15)2.744 (2)3.648 (2)171.6 (19)
C4—H4···F1ii0.982.593.531 (3)162
Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯AD—HH⋯AD⋯AD—H⋯A
N1—H1⋯Cg1i0.911 (15)2.744 (2)3.648 (2)171.6 (19)
C4—H4⋯F1ii0.982.593.531 (3)162

Symmetry codes: (i) ; (ii) . Cg1 is the centroid of the C9–C14 ring.

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Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2012-09-19

3.  Crystal structure of 2,4-bis-(2-chloro-phen-yl)-7-tert-pent-yl-3-aza-bicyclo[3.3.1]nonan-9-one.

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