(1S,3S)-Methyl 6,7-dimeth-oxy-1-phenyl-1,2,3,4-tetra-hydro-isoquinoline-3-carboxyl-ate.

In the title compound, C(19)H(21)NO(4), an organocatalyst with a tetra-hydro-isoquinoline backbone, the heterocyclic ring assumes a half-boat conformation. The dihedral angle between the aromatic rings is 82.93 (8)°. In the crystal, mol-ecules are linked via N-H⋯O and C-H⋯O hydrogen bonds, forming a layer parallel to (10[Formula: see text]).

Related literature

For related structures, see: Naicker et al. (2010 ▶, 2011 ▶).

Experimental

Crystal data

C19H21NO4

M = 327.37

Monoclinic,

a = 9.3841 (3) Å

b = 6.3453 (2) Å

c = 14.2048 (4) Å

β = 94.475 (2)°

V = 843.25 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 173 K

0.90 × 0.07 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.923, T max = 0.995

4184 measured reflections

2275 independent reflections

2138 reflections with I > 2σ(I)

R int = 0.010

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.082

S = 1.05

2275 reflections

222 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.20 e Å−3

Δρmin = −0.13 e Å−3

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009) ▶; software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811018782/is2714sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811018782/is2714Isup2.hkl

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

C19H21NO4	F(000) = 348
Mr = 327.37	Dx = 1.289 Mg m−3
Monoclinic, P21	Melting point: 371 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 9.3841 (3) Å	Cell parameters from 4184 reflections
b = 6.3453 (2) Å	θ = 2.2–28.3°
c = 14.2048 (4) Å	µ = 0.09 mm−1
β = 94.475 (2)°	T = 173 K
V = 843.25 (4) Å3	Needle, colourless
Z = 2	0.90 × 0.07 × 0.06 mm

Nonius KappaCCD diffractometer	2275 independent reflections
Radiation source: fine-focus sealed tube	2138 reflections with I > 2σ(I)
graphite	Rint = 0.010
φ and ω scans	θmax = 28.3°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.923, Tmax = 0.995	k = −8→8
4184 measured reflections	l = −18→18

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.082	w = 1/[σ2(Fo2) + (0.0478P)2 + 0.1004P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
2275 reflections	Δρmax = 0.20 e Å−3
222 parameters	Δρmin = −0.13 e Å−3
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.014 (4)

Experimental. Half sphere of data collected using COLLECT strategy (Nonius, 2000). Crystal to detector distance = 33 mm; combination of φ and ω scans of 1.0°, 60 s per °, 2 iterations.

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.

	x	y	z	Uiso*/Ueq
O1	0.32761 (13)	0.8193 (2)	0.52227 (9)	0.0421 (3)
O2	0.14691 (13)	0.5304 (2)	0.46573 (8)	0.0377 (3)
O3	0.39059 (11)	−0.1210 (2)	0.96117 (8)	0.0372 (3)
O4	0.15273 (11)	−0.0802 (2)	0.93763 (8)	0.0359 (3)
N1	0.44475 (13)	0.2219 (2)	0.85516 (9)	0.0286 (3)
H1N	0.4969 (18)	0.214 (4)	0.9118 (11)	0.033 (5)*
C1	0.45806 (15)	0.4396 (3)	0.82212 (10)	0.0276 (3)
H1	0.4271	0.5382	0.8715	0.033*
C2	0.36095 (14)	0.4684 (2)	0.73185 (10)	0.0260 (3)
C3	0.38575 (16)	0.6398 (3)	0.67243 (11)	0.0303 (3)
H3	0.4558	0.7420	0.6921	0.036*
C4	0.30923 (16)	0.6610 (3)	0.58571 (11)	0.0309 (3)
C5	0.20784 (15)	0.5077 (3)	0.55602 (10)	0.0299 (3)
C6	0.17693 (14)	0.3466 (3)	0.61690 (10)	0.0273 (3)
H6	0.1036	0.2485	0.5984	0.033*
C7	0.25316 (14)	0.3266 (2)	0.70613 (10)	0.0250 (3)
C8	0.21706 (15)	0.1462 (3)	0.76978 (10)	0.0274 (3)
H8A	0.2446	0.0110	0.7415	0.033*
H8B	0.1127	0.1433	0.7759	0.033*
C9	0.29613 (15)	0.1715 (3)	0.86760 (10)	0.0259 (3)
H9	0.2524	0.2909	0.9011	0.031*
C10	0.28876 (15)	−0.0258 (3)	0.92677 (10)	0.0273 (3)
C11	0.1344 (2)	−0.2585 (3)	0.99879 (13)	0.0423 (4)
H11A	0.0322	−0.2859	1.0025	0.063*
H11B	0.1788	−0.2277	1.0621	0.063*
H11C	0.1799	−0.3829	0.9733	0.063*
C12	0.61296 (15)	0.4843 (3)	0.80537 (10)	0.0291 (3)
C13	0.68782 (16)	0.3487 (3)	0.74980 (11)	0.0374 (4)
H13	0.6419	0.2270	0.7229	0.045*
C14	0.82974 (17)	0.3906 (4)	0.73342 (12)	0.0426 (4)
H14	0.8798	0.2980	0.6951	0.051*
C15	0.89763 (17)	0.5663 (4)	0.77280 (13)	0.0431 (4)
H15	0.9951	0.5924	0.7631	0.052*
C16	0.82347 (18)	0.7041 (3)	0.82631 (13)	0.0419 (4)
H16	0.8695	0.8269	0.8520	0.050*
C17	0.68109 (16)	0.6639 (3)	0.84278 (11)	0.0339 (3)
H17	0.6307	0.7594	0.8796	0.041*
C18	0.43336 (19)	0.9743 (3)	0.54802 (15)	0.0450 (4)
H18A	0.4362	1.0782	0.4972	0.067*
H18B	0.5270	0.9062	0.5585	0.067*
H18C	0.4097	1.0450	0.6061	0.067*
C19	0.0553 (2)	0.3649 (3)	0.43094 (12)	0.0480 (5)
H19A	0.0173	0.3981	0.3664	0.072*
H19B	−0.0238	0.3498	0.4715	0.072*
H19C	0.1094	0.2328	0.4308	0.072*

	U11	U22	U33	U12	U13	U23
O1	0.0381 (6)	0.0362 (7)	0.0523 (7)	−0.0028 (6)	0.0043 (5)	0.0163 (6)
O2	0.0426 (6)	0.0405 (7)	0.0296 (5)	−0.0005 (6)	−0.0009 (4)	0.0067 (5)
O3	0.0353 (6)	0.0404 (7)	0.0356 (6)	0.0093 (6)	0.0002 (4)	0.0060 (5)
O4	0.0313 (5)	0.0380 (7)	0.0380 (6)	−0.0025 (5)	−0.0002 (4)	0.0088 (5)
N1	0.0229 (6)	0.0322 (7)	0.0299 (6)	0.0000 (5)	−0.0032 (5)	0.0002 (6)
C1	0.0234 (6)	0.0302 (8)	0.0290 (7)	−0.0003 (6)	0.0007 (5)	−0.0056 (6)
C2	0.0214 (6)	0.0254 (7)	0.0315 (7)	0.0018 (6)	0.0031 (5)	−0.0026 (6)
C3	0.0237 (6)	0.0251 (7)	0.0422 (8)	0.0006 (6)	0.0023 (5)	−0.0008 (7)
C4	0.0263 (6)	0.0281 (8)	0.0390 (8)	0.0036 (6)	0.0077 (6)	0.0067 (7)
C5	0.0266 (7)	0.0337 (8)	0.0296 (7)	0.0040 (6)	0.0030 (5)	0.0018 (6)
C6	0.0237 (6)	0.0286 (7)	0.0296 (7)	0.0000 (6)	0.0012 (5)	−0.0001 (6)
C7	0.0218 (6)	0.0257 (7)	0.0276 (6)	0.0017 (6)	0.0027 (5)	−0.0004 (6)
C8	0.0243 (6)	0.0284 (7)	0.0289 (7)	−0.0023 (6)	−0.0012 (5)	0.0021 (6)
C9	0.0240 (6)	0.0271 (7)	0.0267 (6)	0.0021 (6)	0.0017 (5)	−0.0016 (6)
C10	0.0302 (7)	0.0291 (8)	0.0223 (6)	0.0015 (6)	0.0008 (5)	−0.0040 (6)
C11	0.0477 (9)	0.0388 (10)	0.0404 (9)	−0.0081 (8)	0.0035 (7)	0.0082 (8)
C12	0.0232 (6)	0.0350 (8)	0.0284 (7)	−0.0005 (6)	−0.0017 (5)	−0.0012 (6)
C13	0.0290 (7)	0.0449 (10)	0.0381 (8)	0.0022 (8)	0.0010 (6)	−0.0077 (8)
C14	0.0299 (7)	0.0590 (12)	0.0394 (8)	0.0068 (8)	0.0068 (6)	−0.0014 (9)
C15	0.0247 (7)	0.0602 (12)	0.0445 (9)	−0.0010 (8)	0.0029 (6)	0.0106 (9)
C16	0.0314 (8)	0.0473 (11)	0.0460 (9)	−0.0093 (8)	−0.0031 (7)	0.0041 (9)
C17	0.0286 (7)	0.0370 (9)	0.0357 (8)	−0.0045 (7)	0.0002 (6)	−0.0014 (7)
C18	0.0414 (9)	0.0287 (9)	0.0673 (12)	−0.0008 (8)	0.0203 (8)	0.0072 (9)
C19	0.0671 (12)	0.0411 (11)	0.0331 (8)	0.0001 (10)	−0.0126 (8)	0.0006 (8)

O1—C4	1.3696 (19)	C8—H8B	0.9900
O1—C18	1.424 (2)	C9—C10	1.512 (2)
O2—C5	1.3704 (18)	C9—H9	1.0000
O2—C19	1.421 (2)	C11—H11A	0.9800
O3—C10	1.2017 (18)	C11—H11B	0.9800
O4—C10	1.3429 (18)	C11—H11C	0.9800
O4—C11	1.445 (2)	C12—C17	1.392 (2)
N1—C9	1.4552 (18)	C12—C13	1.394 (2)
N1—C1	1.467 (2)	C13—C14	1.395 (2)
N1—H1N	0.909 (14)	C13—H13	0.9500
C1—C12	1.5178 (19)	C14—C15	1.380 (3)
C1—C2	1.525 (2)	C14—H14	0.9500
C1—H1	1.0000	C15—C16	1.382 (3)
C2—C7	1.381 (2)	C15—H15	0.9500
C2—C3	1.407 (2)	C16—C17	1.398 (2)
C3—C4	1.383 (2)	C16—H16	0.9500
C3—H3	0.9500	C17—H17	0.9500
C4—C5	1.403 (2)	C18—H18A	0.9800
C5—C6	1.384 (2)	C18—H18B	0.9800
C6—C7	1.4118 (18)	C18—H18C	0.9800
C6—H6	0.9500	C19—H19A	0.9800
C7—C8	1.513 (2)	C19—H19B	0.9800
C8—C9	1.5317 (19)	C19—H19C	0.9800
C8—H8A	0.9900
C4—O1—C18	117.28 (14)	C8—C9—H9	108.9
C5—O2—C19	116.41 (13)	O3—C10—O4	123.84 (15)
C10—O4—C11	115.40 (13)	O3—C10—C9	124.95 (14)
C9—N1—C1	110.63 (12)	O4—C10—C9	111.20 (12)
C9—N1—H1N	109.5 (12)	O4—C11—H11A	109.5
C1—N1—H1N	106.5 (15)	O4—C11—H11B	109.5
N1—C1—C12	109.42 (13)	H11A—C11—H11B	109.5
N1—C1—C2	108.75 (12)	O4—C11—H11C	109.5
C12—C1—C2	111.26 (12)	H11A—C11—H11C	109.5
N1—C1—H1	109.1	H11B—C11—H11C	109.5
C12—C1—H1	109.1	C17—C12—C13	119.00 (14)
C2—C1—H1	109.1	C17—C12—C1	120.67 (14)
C7—C2—C3	119.79 (13)	C13—C12—C1	120.31 (14)
C7—C2—C1	121.43 (13)	C12—C13—C14	120.43 (18)
C3—C2—C1	118.75 (13)	C12—C13—H13	119.8
C4—C3—C2	120.72 (14)	C14—C13—H13	119.8
C4—C3—H3	119.6	C15—C14—C13	120.18 (18)
C2—C3—H3	119.6	C15—C14—H14	119.9
O1—C4—C3	125.04 (15)	C13—C14—H14	119.9
O1—C4—C5	115.36 (14)	C14—C15—C16	119.84 (16)
C3—C4—C5	119.55 (14)	C14—C15—H15	120.1
O2—C5—C6	124.75 (14)	C16—C15—H15	120.1
O2—C5—C4	115.61 (14)	C15—C16—C17	120.37 (18)
C6—C5—C4	119.64 (13)	C15—C16—H16	119.8
C5—C6—C7	120.76 (14)	C17—C16—H16	119.8
C5—C6—H6	119.6	C12—C17—C16	120.14 (16)
C7—C6—H6	119.6	C12—C17—H17	119.9
C2—C7—C6	119.20 (13)	C16—C17—H17	119.9
C2—C7—C8	121.88 (12)	O1—C18—H18A	109.5
C6—C7—C8	118.89 (13)	O1—C18—H18B	109.5
C7—C8—C9	110.34 (12)	H18A—C18—H18B	109.5
C7—C8—H8A	109.6	O1—C18—H18C	109.5
C9—C8—H8A	109.6	H18A—C18—H18C	109.5
C7—C8—H8B	109.6	H18B—C18—H18C	109.5
C9—C8—H8B	109.6	O2—C19—H19A	109.5
H8A—C8—H8B	108.1	O2—C19—H19B	109.5
N1—C9—C10	109.60 (12)	H19A—C19—H19B	109.5
N1—C9—C8	108.29 (11)	O2—C19—H19C	109.5
C10—C9—C8	112.19 (12)	H19A—C19—H19C	109.5
N1—C9—H9	108.9	H19B—C19—H19C	109.5
C10—C9—H9	108.9
C9—N1—C1—C12	−177.34 (12)	C5—C6—C7—C8	−179.14 (14)
C9—N1—C1—C2	−55.63 (14)	C2—C7—C8—C9	9.86 (19)
N1—C1—C2—C7	16.42 (18)	C6—C7—C8—C9	−171.91 (13)
C12—C1—C2—C7	137.00 (14)	C1—N1—C9—C10	−163.99 (11)
N1—C1—C2—C3	−161.44 (13)	C1—N1—C9—C8	73.33 (15)
C12—C1—C2—C3	−40.86 (19)	C7—C8—C9—N1	−46.80 (16)
C7—C2—C3—C4	−4.0 (2)	C7—C8—C9—C10	−167.89 (11)
C1—C2—C3—C4	173.89 (14)	C11—O4—C10—O3	3.2 (2)
C18—O1—C4—C3	−0.3 (2)	C11—O4—C10—C9	−175.80 (13)
C18—O1—C4—C5	−177.71 (14)	N1—C9—C10—O3	2.7 (2)
C2—C3—C4—O1	−178.59 (14)	C8—C9—C10—O3	123.00 (16)
C2—C3—C4—C5	−1.2 (2)	N1—C9—C10—O4	−178.38 (12)
C19—O2—C5—C6	−5.8 (2)	C8—C9—C10—O4	−58.05 (15)
C19—O2—C5—C4	173.61 (15)	N1—C1—C12—C17	−130.54 (15)
O1—C4—C5—O2	3.6 (2)	C2—C1—C12—C17	109.27 (16)
C3—C4—C5—O2	−174.04 (14)	N1—C1—C12—C13	51.37 (18)
O1—C4—C5—C6	−177.03 (13)	C2—C1—C12—C13	−68.82 (19)
C3—C4—C5—C6	5.4 (2)	C17—C12—C13—C14	1.2 (3)
O2—C5—C6—C7	175.00 (14)	C1—C12—C13—C14	179.29 (16)
C4—C5—C6—C7	−4.4 (2)	C12—C13—C14—C15	0.5 (3)
C3—C2—C7—C6	5.0 (2)	C13—C14—C15—C16	−1.9 (3)
C1—C2—C7—C6	−172.82 (13)	C14—C15—C16—C17	1.6 (3)
C3—C2—C7—C8	−176.77 (13)	C13—C12—C17—C16	−1.4 (2)
C1—C2—C7—C8	5.4 (2)	C1—C12—C17—C16	−179.55 (15)
C5—C6—C7—C2	−0.9 (2)	C15—C16—C17—C12	0.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3i	0.91 (2)	2.27 (1)	3.0918 (17)	149 (2)
C1—H1···O3ii	1.00	2.55	3.503 (2)	160
C19—H19B···O2iii	0.98	2.53	3.270 (2)	132

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O3i	0.91 (2)	2.27 (1)	3.0918 (17)	149 (2)
C1—H1⋯O3ii	1.00	2.55	3.503 (2)	160
C19—H19B⋯O2iii	0.98	2.53	3.270 (2)	132

Symmetry codes: (i) ; (ii) ; (iii) .