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Acta Cryst. (2009). E65, o1058    [ doi:10.1107/S1600536809013415 ]

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

Q.-H. Zhang, Q. Xie, J.-M. Wang and Z.-B. Qiu

Abstract top

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 [pi]-[pi] stacking interactions (centroid-centroid distance = 3.962 Å).

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 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).

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 m−3
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 mm−1
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)
graphiteRint = 0.087
φ 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 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 = 1.01(Δ/σ)max < 0.001
2662 reflectionsΔρmax = 0.28 e Å−3
196 parametersΔρmin = −0.20 e Å−3
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 mm−1
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 reflectionsθmax = 25.5°
Refinement top
R[F2 > 2σ(F2)] = 0.046H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.128Δρmax = 0.28 e Å−3
S = 1.01Δρmin = −0.20 e Å−3
2662 reflectionsAbsolute structure: ?
196 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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)
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) 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, °) 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—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, °) top
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.
Table 1
Hydrogen-bond geometry (Å, °) top
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.
Acknowledgements top

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

references
References top

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.