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Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): o1058.
Published online 2009 April 18. doi:  10.1107/S1600536809013415
PMCID: PMC2977739

2-Methyl-1,2,3,4-tetra­hydro­isoquinolin-6-yl N-phenyl­carbamate

Abstract

In the mol­ecule of the title compound, C17H18N2O2, the piperidine ring adopts a half-chair form. The two benzene rings are individually planar and make a dihedral angle of 53.90°. The crystal structure is stabilized by inter­molecular N—H(...)N hydrogen bonds and π–π stacking inter­actions (centroid–centroid distance = 3.962 Å).

Related literature

For a related structure, see: (Li et al., 2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1058-scheme1.jpg

Experimental

Crystal data

  • C17H18N2O2
  • M r = 282.33
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1058-efi1.jpg
  • a = 6.0653 (6) Å
  • b = 15.5540 (17) Å
  • c = 15.1817 (16) Å
  • β = 93.488 (2)°
  • V = 1429.6 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 293 K
  • 0.47 × 0.35 × 0.31 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.958, T max = 0.963
  • 7422 measured reflections
  • 2662 independent reflections
  • 2190 reflections with I > 2σ(I)
  • R int = 0.087

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.128
  • S = 1.02
  • 2662 reflections
  • 196 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL and local programs.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809013415/rk2138sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809013415/rk2138Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was funded in part by the National Natural Science Foundation of China (grant No. 30801435).

supplementary crystallographic information

Comment

In the molecular structure of title compound (Fig.1), the piperidine ring adopts a half–chair form, with atoms N2 and C9 out of the plane defined by the remaining four atoms. The N1—C1 bond length [1.3485 (19) Å] is longer than that (1.32 Å) for a peptide linkage. The N1—C11 bond length [1.4128 (19) Å] is shorter than a normal C—N single bond and longer than a normal C═N bond, probably as a result of electron delocalization, suggesting that the N1—C11 bond participates in the conjugated system of the benzene ring (Li et al., 2006). The two phenyl rings are planar and make a dihedral angle of 53.90°. The crystal structure is stabilized through intermolecular N1—H1···N2i hydrogen bonds [symmetry code (i): 1-x, 1-y,, 1-z] and π–π stacking interactions (Fig.2).

Experimental

The 2–methyl–1,2,3,4–tetrahydroisoquinolin–6–ol (6.13 mmol) was dissolved in anhydrous THF (100 ml), and a piece of Na metal (approximately 10 mg) was added. The mixture was stirred at room temperature for 15 min, then phenylisocyanate (18.48 mmol) was added. The reaction mixture was continuously stirred for 2 h at room temperature and monitored by TLC. The precipitate was filtered off and the filtrate was evaporated to give yellow oil. The 20 ml H2O was added and pH of the aqueous layer was adjusted to 3 by 1 N HCl, washed with Et2O, and then pH was adjusted to 10 by NaHCO3 aqueous solution (approximately 1%). The resulting precipitate was filtered and washed with water three times. A yellow solid (yield 1.50 g, 87%) was obtained, and single crystals suitable for crystallographic analysis were obtained by slow evaporation of an ethanol solution.

Refinement

All C–bound H atoms were positioned geometrically and refined as riding (C—H = 0.93–0.97 Å), with Uiso(H) = 1.2Ueq(C) and the three H atoms of the methyl refined as riding (C—H = 0.98 Å), with Uiso(H) = 1.5Ueq(C). The H atom of the NH group was refined isotropically.

Figures

Fig. 1.
The molecular structure of title compound with the atom numbering scheme. The displacement ellipsoids are drawn at the 50% probability level. H atons are presented as a small spheres of arbitrary radius.
Fig. 2.
A view of the crystal packing, showing the hydrogen–bonding network.

Crystal data

C17H18N2O2F(000) = 600
Mr = 282.33Dx = 1.312 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3056 reflections
a = 6.0653 (6) Åθ = 5.2–55.0°
b = 15.5540 (17) ŵ = 0.09 mm1
c = 15.1817 (16) ÅT = 293 K
β = 93.488 (2)°Block, yellow
V = 1429.6 (3) Å30.47 × 0.35 × 0.31 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer2662 independent reflections
Radiation source: Fine–focus sealed tube2190 reflections with I > 2σ(I)
graphiteRint = 0.087
[var phi] and ω scansθmax = 25.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −7→7
Tmin = 0.958, Tmax = 0.963k = −18→13
7422 measured reflectionsl = −18→18

Refinement

Refinement on F2Secondary atom site location: Difmap
Least-squares matrix: FullHydrogen site location: Geom
R[F2 > 2σ(F2)] = 0.046H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.128w = 1/[σ2(Fo2) + (0.067P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
2662 reflectionsΔρmax = 0.28 e Å3
196 parametersΔρmin = −0.20 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: DirectExtinction coefficient: 0.0090 (19)

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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)

xyzUiso*/Ueq
N10.2614 (2)0.25526 (8)0.60923 (8)0.0413 (3)
N20.4681 (2)0.78297 (8)0.56012 (7)0.0411 (3)
O10.15429 (18)0.36878 (7)0.69300 (7)0.0539 (3)
O20.45190 (18)0.37476 (6)0.61019 (7)0.0508 (3)
C10.2728 (2)0.33563 (10)0.64250 (9)0.0385 (4)
C20.4760 (2)0.46370 (9)0.61918 (9)0.0402 (4)
C30.6718 (2)0.49347 (10)0.65786 (9)0.0438 (4)
H30.77600.45560.68310.053*
C40.7104 (2)0.58098 (10)0.65837 (9)0.0425 (4)
H40.84220.60190.68460.051*
C50.5568 (2)0.63838 (9)0.62065 (8)0.0359 (3)
C60.3585 (2)0.60679 (9)0.58205 (8)0.0349 (3)
C70.3195 (2)0.51930 (10)0.58201 (9)0.0392 (4)
H70.18720.49780.55680.047*
C80.6021 (2)0.73292 (10)0.62511 (10)0.0439 (4)
H8A0.57430.75340.68370.053*
H8B0.75700.74260.61590.053*
C90.2354 (2)0.76007 (10)0.56625 (10)0.0443 (4)
H9A0.14410.79810.52890.053*
H9B0.19460.76750.62660.053*
C100.1941 (2)0.66790 (10)0.53803 (9)0.0415 (4)
H10A0.04640.65130.55240.050*
H10B0.20180.66370.47450.050*
C110.1091 (2)0.19113 (9)0.63109 (8)0.0368 (3)
C12−0.0867 (2)0.20917 (10)0.66984 (9)0.0430 (4)
H12−0.12270.26550.68340.052*
C13−0.2280 (3)0.14259 (11)0.68815 (10)0.0490 (4)
H13−0.35960.15490.71390.059*
C14−0.1782 (3)0.05886 (12)0.66912 (11)0.0555 (5)
H14−0.27370.01470.68260.067*
C150.0147 (3)0.04127 (11)0.62988 (11)0.0555 (4)
H150.0488−0.01510.61560.067*
C160.1585 (3)0.10679 (10)0.61141 (10)0.0456 (4)
H160.28960.09410.58550.055*
C170.4991 (3)0.87447 (10)0.57824 (12)0.0585 (5)
H17A0.41820.90740.53370.088*
H17B0.65330.88840.57800.088*
H17C0.44640.88780.63500.088*
H10.360 (3)0.2430 (11)0.5712 (10)0.052 (5)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0499 (8)0.0326 (7)0.0427 (7)0.0008 (6)0.0133 (6)−0.0001 (5)
N20.0510 (8)0.0318 (7)0.0411 (7)−0.0011 (5)0.0071 (5)−0.0010 (5)
O10.0678 (8)0.0401 (7)0.0561 (7)−0.0014 (5)0.0237 (6)−0.0067 (5)
O20.0557 (7)0.0331 (6)0.0655 (7)−0.0022 (5)0.0203 (6)−0.0032 (5)
C10.0460 (8)0.0331 (8)0.0365 (7)0.0036 (7)0.0036 (6)0.0051 (6)
C20.0511 (9)0.0318 (8)0.0388 (7)−0.0005 (7)0.0119 (6)−0.0001 (6)
C30.0482 (9)0.0428 (9)0.0399 (8)0.0067 (7)−0.0005 (6)0.0041 (6)
C40.0415 (8)0.0469 (10)0.0383 (8)−0.0022 (7)−0.0036 (6)−0.0009 (7)
C50.0393 (8)0.0378 (8)0.0309 (7)−0.0018 (6)0.0043 (6)−0.0017 (6)
C60.0359 (8)0.0380 (8)0.0309 (7)−0.0011 (6)0.0044 (6)−0.0009 (6)
C70.0397 (8)0.0398 (9)0.0381 (7)−0.0057 (6)0.0028 (6)−0.0033 (6)
C80.0430 (8)0.0411 (9)0.0471 (8)−0.0048 (7)−0.0004 (6)−0.0048 (7)
C90.0473 (9)0.0429 (9)0.0425 (8)0.0075 (7)0.0023 (6)0.0006 (7)
C100.0377 (8)0.0441 (9)0.0424 (8)0.0007 (7)0.0010 (6)0.0027 (7)
C110.0434 (8)0.0365 (8)0.0301 (7)0.0010 (6)0.0007 (6)0.0034 (6)
C120.0500 (9)0.0398 (9)0.0395 (8)0.0041 (7)0.0058 (6)0.0024 (6)
C130.0480 (9)0.0564 (11)0.0430 (8)−0.0065 (8)0.0068 (7)0.0005 (7)
C140.0618 (11)0.0503 (11)0.0545 (10)−0.0188 (8)0.0045 (8)−0.0017 (8)
C150.0658 (11)0.0366 (9)0.0640 (10)−0.0070 (8)0.0025 (9)−0.0095 (8)
C160.0483 (9)0.0401 (9)0.0487 (8)0.0003 (7)0.0052 (7)−0.0057 (7)
C170.0793 (13)0.0361 (9)0.0611 (10)−0.0047 (8)0.0132 (9)−0.0054 (8)

Geometric parameters (Å, °)

N1—C11.3485 (19)C8—H8B0.9700
N1—C111.4128 (19)C9—C101.513 (2)
N1—H10.879 (16)C9—H9A0.9700
N2—C171.4596 (19)C9—H9B0.9700
N2—C81.4636 (18)C10—H10A0.9700
N2—C91.464 (2)C10—H10B0.9700
O1—C11.1989 (17)C11—C161.382 (2)
O2—C11.3622 (17)C11—C121.385 (2)
O2—C21.3970 (18)C12—C131.383 (2)
C2—C31.373 (2)C12—H120.9300
C2—C71.379 (2)C13—C141.372 (2)
C3—C41.381 (2)C13—H130.9300
C3—H30.9300C14—C151.372 (2)
C4—C51.389 (2)C14—H140.9300
C4—H40.9300C15—C161.381 (2)
C5—C61.395 (2)C15—H150.9300
C5—C81.497 (2)C16—H160.9300
C6—C71.381 (2)C17—H17A0.9600
C6—C101.505 (2)C17—H17B0.9600
C7—H70.9300C17—H17C0.9600
C8—H8A0.9700
C1—N1—C11125.86 (13)N2—C9—H9A109.5
C1—N1—H1115.2 (11)C10—C9—H9A109.5
C11—N1—H1118.9 (11)N2—C9—H9B109.5
C17—N2—C8109.37 (12)C10—C9—H9B109.5
C17—N2—C9109.81 (12)H9A—C9—H9B108.1
C8—N2—C9109.00 (12)C6—C10—C9112.26 (12)
C1—O2—C2119.22 (11)C6—C10—H10A109.2
O1—C1—N1128.26 (14)C9—C10—H10A109.2
O1—C1—O2124.08 (14)C6—C10—H10B109.2
N1—C1—O2107.64 (12)C9—C10—H10B109.2
C3—C2—C7121.30 (13)H10A—C10—H10B107.9
C3—C2—O2117.29 (13)C16—C11—C12119.11 (14)
C7—C2—O2121.04 (13)C16—C11—N1117.77 (14)
C2—C3—C4118.48 (13)C12—C11—N1123.12 (14)
C2—C3—H3120.8C13—C12—C11119.42 (15)
C4—C3—H3120.8C13—C12—H12120.3
C3—C4—C5121.47 (14)C11—C12—H12120.3
C3—C4—H4119.3C14—C13—C12121.43 (16)
C5—C4—H4119.3C14—C13—H13119.3
C4—C5—C6119.11 (14)C12—C13—H13119.3
C4—C5—C8119.75 (12)C13—C14—C15119.02 (16)
C6—C5—C8121.09 (13)C13—C14—H14120.5
C7—C6—C5119.39 (13)C15—C14—H14120.5
C7—C6—C10120.88 (13)C14—C15—C16120.44 (16)
C5—C6—C10119.70 (13)C14—C15—H15119.8
C2—C7—C6120.26 (13)C16—C15—H15119.8
C2—C7—H7119.9C15—C16—C11120.57 (15)
C6—C7—H7119.9C15—C16—H16119.7
N2—C8—C5113.52 (11)C11—C16—H16119.7
N2—C8—H8A108.9N2—C17—H17A109.5
C5—C8—H8A108.9N2—C17—H17B109.5
N2—C8—H8B108.9H17A—C17—H17B109.5
C5—C8—H8B108.9N2—C17—H17C109.5
H8A—C8—H8B107.7H17A—C17—H17C109.5
N2—C9—C10110.88 (12)H17B—C17—H17C109.5
C11—N1—C1—O1−3.2 (2)C17—N2—C8—C5171.44 (13)
C11—N1—C1—O2175.23 (12)C9—N2—C8—C551.38 (16)
C2—O2—C1—O1−14.8 (2)C4—C5—C8—N2161.06 (13)
C2—O2—C1—N1166.71 (12)C6—C5—C8—N2−21.39 (19)
C1—O2—C2—C3126.45 (14)C17—N2—C9—C10173.79 (12)
C1—O2—C2—C7−60.49 (18)C8—N2—C9—C10−66.42 (15)
C7—C2—C3—C4−0.4 (2)C7—C6—C10—C9164.33 (13)
O2—C2—C3—C4172.59 (12)C5—C6—C10—C9−18.03 (18)
C2—C3—C4—C5−0.2 (2)N2—C9—C10—C648.87 (16)
C3—C4—C5—C60.5 (2)C1—N1—C11—C16−161.74 (14)
C3—C4—C5—C8178.10 (13)C1—N1—C11—C1219.2 (2)
C4—C5—C6—C7−0.1 (2)C16—C11—C12—C130.1 (2)
C8—C5—C6—C7−177.68 (13)N1—C11—C12—C13179.23 (13)
C4—C5—C6—C10−177.79 (12)C11—C12—C13—C140.3 (2)
C8—C5—C6—C104.6 (2)C12—C13—C14—C15−1.0 (2)
C3—C2—C7—C60.8 (2)C13—C14—C15—C161.2 (2)
O2—C2—C7—C6−171.95 (12)C14—C15—C16—C11−0.8 (2)
C5—C6—C7—C2−0.5 (2)C12—C11—C16—C150.1 (2)
C10—C6—C7—C2177.12 (12)N1—C11—C16—C15−179.00 (13)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.879 (16)2.339 (16)3.1886 (18)162.5 (14)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2138).

References

  • Bruker (2000). SMART and SAINT Bruker AXS Inc., Madison, Wisconisin, USA.
  • Li, D.-C., Zhou, W.-Y. & Li, C.-B. (2006). Acta Cryst E62, o66–o67.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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