organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890
Volume 65| Part 5| May 2009| Page o1058

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

aDepartment of Medicinal Chemistry, School of Pharmacy, Fudan University, 138 Yixueyuan Road, Shanghai 200032, People's Republic of China, and bCenter of Analysis & Measurement, Fudan University, 220 Handan Road, Shanghai 200433, People's Republic of China
*Correspondence e-mail: zbqiu@shmu.edu.cn

(Received 8 April 2009; accepted 9 April 2009; online 18 April 2009)

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 ππ stacking inter­actions (centroid–centroid distance = 3.962 Å).

Related literature

For a related structure, see: (Li et al., 2006[Li, D.-C., Zhou, W.-Y. & Li, C.-B. (2006). Acta Cryst. E62, o66-o67.]).

[Scheme 1]

Experimental

Crystal data
  • C17H18N2O2

  • Mr = 282.33

  • Monoclinic, P 21 /c

  • 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.958, Tmax = 0.963

  • 7422 measured reflections

  • 2662 independent reflections

  • 2190 reflections with I > 2σ(I)

  • Rint = 0.087

Refinement
  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯N2i 0.879 (16) 2.339 (16) 3.1886 (18) 162.5 (14)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2000[Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconisin, USA.]); cell refinement: SAINT (Bruker, 2000[Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconisin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL and local programs.

Supporting information


Comment top

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 CN 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 ππ stacking interactions (Fig.2).

Related literature top

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

Experimental top

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 top

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.

Computing details top

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

Figures top
[Figure 1] 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.
[Figure 2] Fig. 2. A view of the crystal packing, showing the hydrogen–bonding network.
2-Methyl-1,2,3,4-tetrahydroisoquinolin-6-yl N-phenylcarbamate top
Crystal data top
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 top
Bruker SMART CCD area-detector
diffractometer
2662 independent reflections
Radiation source: Fine–focus sealed tube2190 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.087
ϕ and ω scansθmax = 25.5°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 77
Tmin = 0.958, Tmax = 0.963k = 1813
7422 measured reflectionsl = 1818
Refinement top
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) = 0.128 w = 1/[σ2(Fo2) + (0.067P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
2662 reflectionsΔρmax = 0.28 e Å3
196 parametersΔρmin = 0.21 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)
Crystal data top
C17H18N2O2V = 1429.6 (3) Å3
Mr = 282.33Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.0653 (6) ŵ = 0.09 mm1
b = 15.5540 (17) ÅT = 293 K
c = 15.1817 (16) Å0.47 × 0.35 × 0.31 mm
β = 93.488 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2662 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2190 reflections with I > 2σ(I)
Tmin = 0.958, Tmax = 0.963Rint = 0.087
7422 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.128H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.28 e Å3
2662 reflectionsΔρmin = 0.21 e Å3
196 parameters
Special details top

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) top
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)
C120.0867 (2)0.20917 (10)0.66984 (9)0.0430 (4)
H120.12270.26550.68340.052*
C130.2280 (3)0.14259 (11)0.68815 (10)0.0490 (4)
H130.35960.15490.71390.059*
C140.1782 (3)0.05886 (12)0.66912 (11)0.0555 (5)
H140.27370.01470.68260.067*
C150.0147 (3)0.04127 (11)0.62988 (11)0.0555 (4)
H150.04880.01510.61560.067*
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) top
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, º) top
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—O13.2 (2)C17—N2—C8—C5171.44 (13)
C11—N1—C1—O2175.23 (12)C9—N2—C8—C551.38 (16)
C2—O2—C1—O114.8 (2)C4—C5—C8—N2161.06 (13)
C2—O2—C1—N1166.71 (12)C6—C5—C8—N221.39 (19)
C1—O2—C2—C3126.45 (14)C17—N2—C9—C10173.79 (12)
C1—O2—C2—C760.49 (18)C8—N2—C9—C1066.42 (15)
C7—C2—C3—C40.4 (2)C7—C6—C10—C9164.33 (13)
O2—C2—C3—C4172.59 (12)C5—C6—C10—C918.03 (18)
C2—C3—C4—C50.2 (2)N2—C9—C10—C648.87 (16)
C3—C4—C5—C60.5 (2)C1—N1—C11—C16161.74 (14)
C3—C4—C5—C8178.10 (13)C1—N1—C11—C1219.2 (2)
C4—C5—C6—C70.1 (2)C16—C11—C12—C130.1 (2)
C8—C5—C6—C7177.68 (13)N1—C11—C12—C13179.23 (13)
C4—C5—C6—C10177.79 (12)C11—C12—C13—C140.3 (2)
C8—C5—C6—C104.6 (2)C12—C13—C14—C151.0 (2)
C3—C2—C7—C60.8 (2)C13—C14—C15—C161.2 (2)
O2—C2—C7—C6171.95 (12)C14—C15—C16—C110.8 (2)
C5—C6—C7—C20.5 (2)C12—C11—C16—C150.1 (2)
C10—C6—C7—C2177.12 (12)N1—C11—C16—C15179.00 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.879 (16)2.339 (16)3.1886 (18)162.5 (14)
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC17H18N2O2
Mr282.33
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)6.0653 (6), 15.5540 (17), 15.1817 (16)
β (°) 93.488 (2)
V3)1429.6 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.47 × 0.35 × 0.31
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.958, 0.963
No. of measured, independent and
observed [I > 2σ(I)] reflections
7422, 2662, 2190
Rint0.087
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.128, 1.02
No. of reflections2662
No. of parameters196
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.28, 0.21

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and local programs.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.879 (16)2.339 (16)3.1886 (18)162.5 (14)
Symmetry code: (i) x+1, y+1, z+1.
 

Acknowledgements

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

References

First citationBruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconisin, USA.  Google Scholar
First citationLi, D.-C., Zhou, W.-Y. & Li, C.-B. (2006). Acta Cryst. E62, o66–o67.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

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ISSN: 2056-9890
Volume 65| Part 5| May 2009| Page o1058
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