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

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

doi:10.1107/S1600536809013415

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1058

doi:10.1107/S1600536809013415

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

Qi-Hong Zhang,^a Qiong Xie,^a Jing-Mei Wang ^b and Zhui-Bai Qiu ^a ^*

^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 π–π stacking interactions (centroid–centroid distance = 3.962 Å).

Related literature

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

Experimental

Crystal data

C₁₇H₁₈N₂O₂
M_r = 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 ) 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[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
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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 and local programs.

Supporting information

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

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

checkCIF report

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 NaHCO₃aqueous 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.

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

	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.

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

Crystal data top

C₁₇H₁₈N₂O₂	F(000) = 600
M_r = 282.33	D_x = 1.312 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3056 reflections
a = 6.0653 (6) Å	θ = 5.2–55.0°
b = 15.5540 (17) Å	µ = 0.09 mm⁻¹
c = 15.1817 (16) Å	T = 293 K
β = 93.488 (2)°	Block, yellow
V = 1429.6 (3) Å³	0.47 × 0.35 × 0.31 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2662 independent reflections
Radiation source: Fine–focus sealed tube	2190 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.087
ϕ and ω scans	θ_max = 25.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.958, T_max = 0.963	k = −18→13
7422 measured reflections	l = −18→18

Refinement top

Refinement on F²	Secondary atom site location: Difmap
Least-squares matrix: Full	Hydrogen site location: Geom
R[F² > 2σ(F²)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.128	w = 1/[σ²(F_o²) + (0.067P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2662 reflections	Δρ_max = 0.28 e Å⁻³
196 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: Direct	Extinction coefficient: 0.0090 (19)

Crystal data top

C₁₇H₁₈N₂O₂	V = 1429.6 (3) Å³
M_r = 282.33	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.0653 (6) Å	µ = 0.09 mm⁻¹
b = 15.5540 (17) Å	T = 293 K
c = 15.1817 (16) Å	0.47 × 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)
T_min = 0.958, T_max = 0.963	R_int = 0.087
7422 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.28 e Å⁻³
2662 reflections	Δρ_min = −0.21 e Å⁻³
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

	x	y	z	U_iso*/U_eq
N1	0.2614 (2)	0.25526 (8)	0.60923 (8)	0.0413 (3)
N2	0.4681 (2)	0.78297 (8)	0.56012 (7)	0.0411 (3)
O1	0.15429 (18)	0.36878 (7)	0.69300 (7)	0.0539 (3)
O2	0.45190 (18)	0.37476 (6)	0.61019 (7)	0.0508 (3)
C1	0.2728 (2)	0.33563 (10)	0.64250 (9)	0.0385 (4)
C2	0.4760 (2)	0.46370 (9)	0.61918 (9)	0.0402 (4)
C3	0.6718 (2)	0.49347 (10)	0.65786 (9)	0.0438 (4)
H3	0.7760	0.4556	0.6831	0.053*
C4	0.7104 (2)	0.58098 (10)	0.65837 (9)	0.0425 (4)
H4	0.8422	0.6019	0.6846	0.051*
C5	0.5568 (2)	0.63838 (9)	0.62065 (8)	0.0359 (3)
C6	0.3585 (2)	0.60679 (9)	0.58205 (8)	0.0349 (3)
C7	0.3195 (2)	0.51930 (10)	0.58201 (9)	0.0392 (4)
H7	0.1872	0.4978	0.5568	0.047*
C8	0.6021 (2)	0.73292 (10)	0.62511 (10)	0.0439 (4)
H8A	0.5743	0.7534	0.6837	0.053*
H8B	0.7570	0.7426	0.6159	0.053*
C9	0.2354 (2)	0.76007 (10)	0.56625 (10)	0.0443 (4)
H9A	0.1441	0.7981	0.5289	0.053*
H9B	0.1946	0.7675	0.6266	0.053*
C10	0.1941 (2)	0.66790 (10)	0.53803 (9)	0.0415 (4)
H10A	0.0464	0.6513	0.5524	0.050*
H10B	0.2018	0.6637	0.4745	0.050*
C11	0.1091 (2)	0.19113 (9)	0.63109 (8)	0.0368 (3)
C12	−0.0867 (2)	0.20917 (10)	0.66984 (9)	0.0430 (4)
H12	−0.1227	0.2655	0.6834	0.052*
C13	−0.2280 (3)	0.14259 (11)	0.68815 (10)	0.0490 (4)
H13	−0.3596	0.1549	0.7139	0.059*
C14	−0.1782 (3)	0.05886 (12)	0.66912 (11)	0.0555 (5)
H14	−0.2737	0.0147	0.6826	0.067*
C15	0.0147 (3)	0.04127 (11)	0.62988 (11)	0.0555 (4)
H15	0.0488	−0.0151	0.6156	0.067*
C16	0.1585 (3)	0.10679 (10)	0.61141 (10)	0.0456 (4)
H16	0.2896	0.0941	0.5855	0.055*
C17	0.4991 (3)	0.87447 (10)	0.57824 (12)	0.0585 (5)
H17A	0.4182	0.9074	0.5337	0.088*
H17B	0.6533	0.8884	0.5780	0.088*
H17C	0.4464	0.8878	0.6350	0.088*
H1	0.360 (3)	0.2430 (11)	0.5712 (10)	0.052 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0499 (8)	0.0326 (7)	0.0427 (7)	0.0008 (6)	0.0133 (6)	−0.0001 (5)
N2	0.0510 (8)	0.0318 (7)	0.0411 (7)	−0.0011 (5)	0.0071 (5)	−0.0010 (5)
O1	0.0678 (8)	0.0401 (7)	0.0561 (7)	−0.0014 (5)	0.0237 (6)	−0.0067 (5)
O2	0.0557 (7)	0.0331 (6)	0.0655 (7)	−0.0022 (5)	0.0203 (6)	−0.0032 (5)
C1	0.0460 (8)	0.0331 (8)	0.0365 (7)	0.0036 (7)	0.0036 (6)	0.0051 (6)
C2	0.0511 (9)	0.0318 (8)	0.0388 (7)	−0.0005 (7)	0.0119 (6)	−0.0001 (6)
C3	0.0482 (9)	0.0428 (9)	0.0399 (8)	0.0067 (7)	−0.0005 (6)	0.0041 (6)
C4	0.0415 (8)	0.0469 (10)	0.0383 (8)	−0.0022 (7)	−0.0036 (6)	−0.0009 (7)
C5	0.0393 (8)	0.0378 (8)	0.0309 (7)	−0.0018 (6)	0.0043 (6)	−0.0017 (6)
C6	0.0359 (8)	0.0380 (8)	0.0309 (7)	−0.0011 (6)	0.0044 (6)	−0.0009 (6)
C7	0.0397 (8)	0.0398 (9)	0.0381 (7)	−0.0057 (6)	0.0028 (6)	−0.0033 (6)
C8	0.0430 (8)	0.0411 (9)	0.0471 (8)	−0.0048 (7)	−0.0004 (6)	−0.0048 (7)
C9	0.0473 (9)	0.0429 (9)	0.0425 (8)	0.0075 (7)	0.0023 (6)	0.0006 (7)
C10	0.0377 (8)	0.0441 (9)	0.0424 (8)	0.0007 (7)	0.0010 (6)	0.0027 (7)
C11	0.0434 (8)	0.0365 (8)	0.0301 (7)	0.0010 (6)	0.0007 (6)	0.0034 (6)
C12	0.0500 (9)	0.0398 (9)	0.0395 (8)	0.0041 (7)	0.0058 (6)	0.0024 (6)
C13	0.0480 (9)	0.0564 (11)	0.0430 (8)	−0.0065 (8)	0.0068 (7)	0.0005 (7)
C14	0.0618 (11)	0.0503 (11)	0.0545 (10)	−0.0188 (8)	0.0045 (8)	−0.0017 (8)
C15	0.0658 (11)	0.0366 (9)	0.0640 (10)	−0.0070 (8)	0.0025 (9)	−0.0095 (8)
C16	0.0483 (9)	0.0401 (9)	0.0487 (8)	0.0003 (7)	0.0052 (7)	−0.0057 (7)
C17	0.0793 (13)	0.0361 (9)	0.0611 (10)	−0.0047 (8)	0.0132 (9)	−0.0054 (8)

Geometric parameters (Å, º) top

N1—C1	1.3485 (19)	C8—H8B	0.9700
N1—C11	1.4128 (19)	C9—C10	1.513 (2)
N1—H1	0.879 (16)	C9—H9A	0.9700
N2—C17	1.4596 (19)	C9—H9B	0.9700
N2—C8	1.4636 (18)	C10—H10A	0.9700
N2—C9	1.464 (2)	C10—H10B	0.9700
O1—C1	1.1989 (17)	C11—C16	1.382 (2)
O2—C1	1.3622 (17)	C11—C12	1.385 (2)
O2—C2	1.3970 (18)	C12—C13	1.383 (2)
C2—C3	1.373 (2)	C12—H12	0.9300
C2—C7	1.379 (2)	C13—C14	1.372 (2)
C3—C4	1.381 (2)	C13—H13	0.9300
C3—H3	0.9300	C14—C15	1.372 (2)
C4—C5	1.389 (2)	C14—H14	0.9300
C4—H4	0.9300	C15—C16	1.381 (2)
C5—C6	1.395 (2)	C15—H15	0.9300
C5—C8	1.497 (2)	C16—H16	0.9300
C6—C7	1.381 (2)	C17—H17A	0.9600
C6—C10	1.505 (2)	C17—H17B	0.9600
C7—H7	0.9300	C17—H17C	0.9600
C8—H8A	0.9700

C1—N1—C11	125.86 (13)	N2—C9—H9A	109.5
C1—N1—H1	115.2 (11)	C10—C9—H9A	109.5
C11—N1—H1	118.9 (11)	N2—C9—H9B	109.5
C17—N2—C8	109.37 (12)	C10—C9—H9B	109.5
C17—N2—C9	109.81 (12)	H9A—C9—H9B	108.1
C8—N2—C9	109.00 (12)	C6—C10—C9	112.26 (12)
C1—O2—C2	119.22 (11)	C6—C10—H10A	109.2
O1—C1—N1	128.26 (14)	C9—C10—H10A	109.2
O1—C1—O2	124.08 (14)	C6—C10—H10B	109.2
N1—C1—O2	107.64 (12)	C9—C10—H10B	109.2
C3—C2—C7	121.30 (13)	H10A—C10—H10B	107.9
C3—C2—O2	117.29 (13)	C16—C11—C12	119.11 (14)
C7—C2—O2	121.04 (13)	C16—C11—N1	117.77 (14)
C2—C3—C4	118.48 (13)	C12—C11—N1	123.12 (14)
C2—C3—H3	120.8	C13—C12—C11	119.42 (15)
C4—C3—H3	120.8	C13—C12—H12	120.3
C3—C4—C5	121.47 (14)	C11—C12—H12	120.3
C3—C4—H4	119.3	C14—C13—C12	121.43 (16)
C5—C4—H4	119.3	C14—C13—H13	119.3
C4—C5—C6	119.11 (14)	C12—C13—H13	119.3
C4—C5—C8	119.75 (12)	C13—C14—C15	119.02 (16)
C6—C5—C8	121.09 (13)	C13—C14—H14	120.5
C7—C6—C5	119.39 (13)	C15—C14—H14	120.5
C7—C6—C10	120.88 (13)	C14—C15—C16	120.44 (16)
C5—C6—C10	119.70 (13)	C14—C15—H15	119.8
C2—C7—C6	120.26 (13)	C16—C15—H15	119.8
C2—C7—H7	119.9	C15—C16—C11	120.57 (15)
C6—C7—H7	119.9	C15—C16—H16	119.7
N2—C8—C5	113.52 (11)	C11—C16—H16	119.7
N2—C8—H8A	108.9	N2—C17—H17A	109.5
C5—C8—H8A	108.9	N2—C17—H17B	109.5
N2—C8—H8B	108.9	H17A—C17—H17B	109.5
C5—C8—H8B	108.9	N2—C17—H17C	109.5
H8A—C8—H8B	107.7	H17A—C17—H17C	109.5
N2—C9—C10	110.88 (12)	H17B—C17—H17C	109.5

C11—N1—C1—O1	−3.2 (2)	C17—N2—C8—C5	171.44 (13)
C11—N1—C1—O2	175.23 (12)	C9—N2—C8—C5	51.38 (16)
C2—O2—C1—O1	−14.8 (2)	C4—C5—C8—N2	161.06 (13)
C2—O2—C1—N1	166.71 (12)	C6—C5—C8—N2	−21.39 (19)
C1—O2—C2—C3	126.45 (14)	C17—N2—C9—C10	173.79 (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—C9	164.33 (13)
O2—C2—C3—C4	172.59 (12)	C5—C6—C10—C9	−18.03 (18)
C2—C3—C4—C5	−0.2 (2)	N2—C9—C10—C6	48.87 (16)
C3—C4—C5—C6	0.5 (2)	C1—N1—C11—C16	−161.74 (14)
C3—C4—C5—C8	178.10 (13)	C1—N1—C11—C12	19.2 (2)
C4—C5—C6—C7	−0.1 (2)	C16—C11—C12—C13	0.1 (2)
C8—C5—C6—C7	−177.68 (13)	N1—C11—C12—C13	179.23 (13)
C4—C5—C6—C10	−177.79 (12)	C11—C12—C13—C14	0.3 (2)
C8—C5—C6—C10	4.6 (2)	C12—C13—C14—C15	−1.0 (2)
C3—C2—C7—C6	0.8 (2)	C13—C14—C15—C16	1.2 (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—C15	0.1 (2)
C10—C6—C7—C2	177.12 (12)	N1—C11—C16—C15	−179.00 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₈N₂O₂
M_r	282.33
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.0653 (6), 15.5540 (17), 15.1817 (16)
β (°)	93.488 (2)
V (Å³)	1429.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.47 × 0.35 × 0.31

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.958, 0.963
No. of measured, independent and observed [I > 2σ(I)] reflections	7422, 2662, 2190
R_int	0.087
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.128, 1.02
No. of reflections	2662
No. of parameters	196
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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.

Acknowledgements

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

References

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