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In the title mol­ecule, C21H23NO2, the phenyl ring and the fused benzene ring of the naphthyl system form a dihedral angle of 64.22 (5) Å. The cyclo­hexene ring is in a half-chair conformation. In the crystal structure, mol­ecules are linked into one-dimensional chains in the b-axis direction via inter­molecular N—H...O [N...O = 3.3517 (15) Å] hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039747/bt6794sup1.cif
Contains datablocks global, 2

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039747/bt67942sup2.hkl
Contains datablock 2

CCDC reference: 296524

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.045
  • wR factor = 0.126
  • Data-to-parameter ratio = 17.9

checkCIF/PLATON results

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Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.824 0.991 Tmin(prime) and Tmax expected: 0.964 0.986 RR(prime) = 0.850 Please check that your absorption correction is appropriate. PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.85
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The addition of carbon-based nucleophiles to activated alkenes represents one of the fundamental methods for the controlled construction of carbon–carbon bonds in organic synthesis. To this end, we have reported that heterobicyclic alkenes are effective substrates for metal-catalysed ring-opening reactions with a variety of nucleophiles (for a review, see: Lautens, Fagnou & Hiebert, 2003). One example of such a reaction is the Pd(II)-catalysed ring-opening addition of boronic acids to heterobicyclic alkenes (Lautens & Dockendorff, 2003). This reaction is particularly useful for the synthesis of 1-aminotetralin scaffolds via the ring-opening of azabicyclic alkenes such as (1). Here we report the crystal structure of dihydronaphthalene (2) derived from the Pd(II)-catalysed ring-opening of azabicycle (1) with phenylboronic acid.

The title molecule is shown in Fig. 1. A l l bond lengths and angles are within the expected ranges (Allen et al., 1987). The benzene ring of the naphthalen-1-yl moiety (C2–C7) and the phenyl ring (C11–C16) form a dihedral angle of 64.22 (5)°. In the cyclohexene ring the atoms C2, C7, C8 and C9 form a plane with an r.m.s. deviation 0.023 Å, while atoms C1 and C10 are −0.225 (3) and 0.203 (3) Å from this plane respectively. The conformation analysis of that ring (Duax et al., 1976) shows that the conformation is a half-chair, with a local pseudo-twofold axis running through the midpoints of the C7—C8 and C1—C10 bonds. In the crystal structure, molecules related by unit-cell translations are linked via intermolecular N—H···O hydrogen bonds to form extended C4 chains (Bernstein et al., 1995) in the b-axis direction (Table 1 and Fig. 1).

Experimental top

Azabicycle (1) (5 g, 20.55 mmol), phenylboronic acid (3.76 g, 30.84 mmol), and (bis-1,3-diphenylphosphinopropane)palladium(II)dichloride (0.121 g, 0.205 mmol, 0.01 eq.) were added to a 250 ml round-bottom flask with stir bar. The flask was sealed with a septum and evacuated/flushed with nitrogen three times. Methanol (75 ml) was added by syringe, followed by saturated aqueous solution of Cs2CO3 (5M, 4.1 ml, 1 eq.). The flask was put in an oil bath at 333 K and the reaction was heated for 1.5 h, after which time NMR analysis indicated that reaction was complete. The reaction was adsorbed onto a minimum amount of silica gel and purified by flash column (4" x 6" silica gel, eluted with 2–10% EtOAc/hexanes). Yield = 98%. X-ray quality crystals were obtained from an analogous reaction on a smaller scale. The crude reaction mixture, still as a solution in methanol, was stored in a sealed flask in a 258 K freezer for an extended period, after which time crystallization occurred.

Refinement top

H atoms were included in the refinement in geometric positions, with C—H distances ranging from 0.95 to 1.00 Å, and an N—H distance of 0.88 Å. They were included in the refinement in riding-motion approximation with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(C) for methyl H atoms.

Computing details top

Data collection: COLLECT (Nonius, 2003); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL/PC (Sheldrick, 2001); molecular graphics: SHELXTL/PC; software used to prepare material for publication: SHELXTL/PC.

Figures top
[Figure 1] Fig. 1. View of (2), showing 30% probability displacement ellipsoids. (arbitrary spheres for the H atoms).
[Figure 2] Fig. 2. A partial packing plot (Spek, 2003) of (2), showing hydrogen bonds as dashed lines.
tert-Butyl (2-phenyl-1,2-dihydro-1-naphthyl)carbamate top
Crystal data top
C21H23NO2F(000) = 1376
Mr = 321.40Dx = 1.224 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 12640 reflections
a = 29.4222 (10) Åθ = 3.2–27.5°
b = 5.4655 (1) ŵ = 0.08 mm1
c = 21.7842 (7) ÅT = 150 K
β = 95.4570 (13)°Needle, colourless
V = 3487.18 (18) Å30.46 × 0.22 × 0.18 mm
Z = 8
Data collection top
Bruker–Nonius KappaCCD
diffractometer
3901 independent reflections
Radiation source: fine-focus sealed tube2869 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
Detector resolution: 9 pixels mm-1θmax = 27.5°, θmin = 3.2°
ϕ scans and ω scans with κ offsetsh = 3837
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
k = 67
Tmin = 0.824, Tmax = 0.991l = 2528
12640 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)] = 0.045H-atom parameters constrained
wR(F2) = 0.126 w = 1/[σ2(Fo2) + (0.0567P)2 + 1.1855P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
3901 reflectionsΔρmax = 0.17 e Å3
218 parametersΔρmin = 0.15 e Å3
0 restraintsExtinction correction: SHELXTL/PC, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0085 (13)
Crystal data top
C21H23NO2V = 3487.18 (18) Å3
Mr = 321.40Z = 8
Monoclinic, C2/cMo Kα radiation
a = 29.4222 (10) ŵ = 0.08 mm1
b = 5.4655 (1) ÅT = 150 K
c = 21.7842 (7) Å0.46 × 0.22 × 0.18 mm
β = 95.4570 (13)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer
3901 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
2869 reflections with I > 2σ(I)
Tmin = 0.824, Tmax = 0.991Rint = 0.042
12640 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.126H-atom parameters constrained
S = 1.02Δρmax = 0.17 e Å3
3901 reflectionsΔρmin = 0.15 e Å3
218 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
O10.85856 (4)0.25880 (18)0.61630 (5)0.0543 (3)
O20.85041 (3)0.05403 (16)0.68345 (4)0.0451 (3)
N10.86220 (4)0.1397 (2)0.58723 (5)0.0406 (3)
H1A0.85800.29280.59780.049*
C10.87440 (4)0.0824 (2)0.52536 (6)0.0391 (3)
H1B0.87840.09910.52390.047*
C20.83505 (4)0.1441 (2)0.47747 (6)0.0395 (3)
C30.79637 (5)0.0027 (3)0.47230 (7)0.0497 (4)
H3A0.79550.14490.49730.060*
C40.75908 (5)0.0545 (3)0.43148 (7)0.0566 (4)
H4A0.73290.04840.42820.068*
C50.75992 (5)0.2612 (3)0.39560 (7)0.0541 (4)
H5A0.73430.30150.36760.065*
C60.79787 (5)0.4095 (3)0.40024 (6)0.0498 (4)
H6A0.79800.55320.37570.060*
C70.83619 (5)0.3519 (2)0.44045 (6)0.0407 (3)
C80.87733 (5)0.5035 (3)0.44443 (7)0.0507 (4)
H8A0.87670.65420.42260.061*
C90.91561 (5)0.4371 (3)0.47759 (7)0.0500 (4)
H9A0.94090.54630.48050.060*
C100.92049 (5)0.1962 (3)0.51068 (6)0.0463 (3)
H10A0.93330.08070.48110.056*
C110.95539 (5)0.2051 (3)0.56659 (6)0.0466 (3)
C120.95671 (5)0.3987 (3)0.60785 (7)0.0576 (4)
H12A0.93560.52940.60080.069*
C130.98823 (6)0.4046 (4)0.65906 (8)0.0683 (5)
H13A0.98830.53780.68710.082*
C141.01947 (6)0.2192 (4)0.66969 (8)0.0699 (5)
H14A1.04140.22430.70460.084*
C151.01869 (6)0.0261 (4)0.62926 (8)0.0676 (5)
H15A1.04020.10290.63620.081*
C160.98679 (5)0.0185 (3)0.57846 (7)0.0550 (4)
H16A0.98640.11730.55120.066*
C170.85738 (4)0.0414 (2)0.62807 (6)0.0390 (3)
C180.84493 (5)0.1084 (2)0.73637 (6)0.0440 (3)
C190.84020 (7)0.0726 (3)0.78792 (7)0.0635 (5)
H19A0.81270.17150.77820.095*
H19B0.86700.17960.79230.095*
H19C0.83780.01610.82660.095*
C200.88728 (6)0.2651 (3)0.75037 (8)0.0627 (4)
H20A0.88980.38130.71660.094*
H20B0.88500.35510.78890.094*
H20C0.91440.16010.75470.094*
C210.80191 (6)0.2603 (3)0.72409 (8)0.0622 (4)
H21A0.80580.37720.69090.093*
H21B0.77600.15250.71180.093*
H21C0.79610.34930.76160.093*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0777 (7)0.0401 (6)0.0467 (6)0.0025 (5)0.0135 (5)0.0024 (4)
O20.0615 (6)0.0412 (5)0.0341 (5)0.0002 (4)0.0117 (4)0.0039 (4)
N10.0484 (6)0.0391 (6)0.0356 (6)0.0041 (5)0.0098 (5)0.0034 (4)
C10.0422 (7)0.0418 (7)0.0341 (7)0.0053 (5)0.0075 (5)0.0018 (5)
C20.0435 (7)0.0421 (7)0.0337 (6)0.0048 (5)0.0077 (5)0.0012 (5)
C30.0499 (8)0.0537 (8)0.0461 (8)0.0021 (6)0.0071 (6)0.0059 (6)
C40.0458 (8)0.0698 (10)0.0540 (9)0.0057 (7)0.0039 (7)0.0007 (8)
C50.0489 (8)0.0687 (10)0.0439 (8)0.0105 (7)0.0005 (6)0.0011 (7)
C60.0604 (9)0.0494 (8)0.0389 (8)0.0106 (7)0.0013 (6)0.0035 (6)
C70.0490 (7)0.0405 (7)0.0328 (7)0.0048 (6)0.0054 (5)0.0028 (5)
C80.0653 (9)0.0450 (8)0.0415 (8)0.0034 (7)0.0031 (7)0.0058 (6)
C90.0530 (8)0.0546 (8)0.0434 (8)0.0092 (7)0.0091 (6)0.0047 (6)
C100.0423 (7)0.0564 (8)0.0411 (7)0.0032 (6)0.0089 (6)0.0012 (6)
C110.0394 (7)0.0579 (8)0.0437 (7)0.0024 (6)0.0093 (6)0.0043 (6)
C120.0568 (9)0.0616 (10)0.0538 (9)0.0108 (7)0.0027 (7)0.0021 (7)
C130.0722 (11)0.0751 (12)0.0563 (10)0.0039 (9)0.0016 (8)0.0111 (8)
C140.0600 (10)0.0895 (13)0.0571 (10)0.0083 (9)0.0107 (8)0.0010 (9)
C150.0574 (10)0.0786 (12)0.0652 (11)0.0192 (8)0.0023 (8)0.0061 (9)
C160.0512 (9)0.0610 (9)0.0530 (9)0.0082 (7)0.0054 (7)0.0001 (7)
C170.0393 (7)0.0417 (7)0.0363 (7)0.0023 (5)0.0053 (5)0.0026 (5)
C180.0559 (8)0.0424 (7)0.0341 (7)0.0039 (6)0.0063 (6)0.0067 (5)
C190.0970 (13)0.0553 (9)0.0408 (8)0.0065 (8)0.0192 (8)0.0005 (7)
C200.0696 (10)0.0620 (10)0.0539 (9)0.0065 (8)0.0070 (8)0.0078 (8)
C210.0638 (10)0.0706 (11)0.0528 (9)0.0185 (8)0.0089 (7)0.0080 (8)
Geometric parameters (Å, º) top
O1—C171.2166 (16)C10—H10A1.0000
O2—C171.3479 (15)C11—C161.384 (2)
O2—C181.4759 (15)C11—C121.386 (2)
N1—C171.3474 (16)C12—C131.382 (2)
N1—C11.4613 (16)C12—H12A0.9500
N1—H1A0.8800C13—C141.373 (3)
C1—C21.5208 (18)C13—H13A0.9500
C1—C101.5525 (18)C14—C151.373 (3)
C1—H1B1.0000C14—H14A0.9500
C2—C31.3880 (19)C15—C161.382 (2)
C2—C71.3954 (18)C15—H15A0.9500
C3—C41.381 (2)C16—H16A0.9500
C3—H3A0.9500C18—C191.513 (2)
C4—C51.375 (2)C18—C211.516 (2)
C4—H4A0.9500C18—C201.519 (2)
C5—C61.376 (2)C19—H19A0.9800
C5—H5A0.9500C19—H19B0.9800
C6—C71.3963 (19)C19—H19C0.9800
C6—H6A0.9500C20—H20A0.9800
C7—C81.463 (2)C20—H20B0.9800
C8—C91.329 (2)C20—H20C0.9800
C8—H8A0.9500C21—H21A0.9800
C9—C101.502 (2)C21—H21B0.9800
C9—H9A0.9500C21—H21C0.9800
C10—C111.517 (2)
C17—O2—C18120.23 (10)C13—C12—C11121.11 (15)
C17—N1—C1120.15 (11)C13—C12—H12A119.4
C17—N1—H1A119.9C11—C12—H12A119.4
C1—N1—H1A119.9C14—C13—C12120.40 (17)
N1—C1—C2110.33 (10)C14—C13—H13A119.8
N1—C1—C10113.59 (11)C12—C13—H13A119.8
C2—C1—C10113.14 (10)C13—C14—C15119.27 (16)
N1—C1—H1B106.4C13—C14—H14A120.4
C2—C1—H1B106.4C15—C14—H14A120.4
C10—C1—H1B106.4C14—C15—C16120.35 (16)
C3—C2—C7119.23 (12)C14—C15—H15A119.8
C3—C2—C1119.50 (12)C16—C15—H15A119.8
C7—C2—C1121.21 (12)C15—C16—C11121.21 (15)
C4—C3—C2121.09 (14)C15—C16—H16A119.4
C4—C3—H3A119.5C11—C16—H16A119.4
C2—C3—H3A119.5O1—C17—N1124.84 (12)
C5—C4—C3119.73 (14)O1—C17—O2125.20 (12)
C5—C4—H4A120.1N1—C17—O2109.95 (11)
C3—C4—H4A120.1O2—C18—C19102.18 (11)
C4—C5—C6120.03 (14)O2—C18—C21110.05 (11)
C4—C5—H5A120.0C19—C18—C21110.78 (13)
C6—C5—H5A120.0O2—C18—C20110.34 (11)
C5—C6—C7120.99 (14)C19—C18—C20110.56 (13)
C5—C6—H6A119.5C21—C18—C20112.45 (13)
C7—C6—H6A119.5C18—C19—H19A109.5
C2—C7—C6118.91 (13)C18—C19—H19B109.5
C2—C7—C8119.49 (12)H19A—C19—H19B109.5
C6—C7—C8121.60 (13)C18—C19—H19C109.5
C9—C8—C7122.09 (13)H19A—C19—H19C109.5
C9—C8—H8A119.0H19B—C19—H19C109.5
C7—C8—H8A119.0C18—C20—H20A109.5
C8—C9—C10122.52 (13)C18—C20—H20B109.5
C8—C9—H9A118.7H20A—C20—H20B109.5
C10—C9—H9A118.7C18—C20—H20C109.5
C9—C10—C11112.57 (12)H20A—C20—H20C109.5
C9—C10—C1113.87 (11)H20B—C20—H20C109.5
C11—C10—C1112.64 (11)C18—C21—H21A109.5
C9—C10—H10A105.6C18—C21—H21B109.5
C11—C10—H10A105.6H21A—C21—H21B109.5
C1—C10—H10A105.6C18—C21—H21C109.5
C16—C11—C12117.65 (14)H21A—C21—H21C109.5
C16—C11—C10121.01 (13)H21B—C21—H21C109.5
C12—C11—C10121.34 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.882.483.3517 (15)169
Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC21H23NO2
Mr321.40
Crystal system, space groupMonoclinic, C2/c
Temperature (K)150
a, b, c (Å)29.4222 (10), 5.4655 (1), 21.7842 (7)
β (°) 95.4570 (13)
V3)3487.18 (18)
Z8
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.46 × 0.22 × 0.18
Data collection
DiffractometerBruker–Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995)
Tmin, Tmax0.824, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections
12640, 3901, 2869
Rint0.042
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.126, 1.02
No. of reflections3901
No. of parameters218
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.17, 0.15

Computer programs: COLLECT (Nonius, 2003), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SIR92 (Altomare et al., 1994), SHELXTL/PC (Sheldrick, 2001), SHELXTL/PC.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.882.483.3517 (15)169
Symmetry code: (i) x, y+1, z.
 

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