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

The title compound, C(20)H(23)NO(5), is the third in a series of tetra-hydoisoquinoline (TIQ) compounds that are precursors to novel chiral catalysts. The N-containing six-membered ring assumes a half-boat conformation. No hydrogen bonding is observed in the crystal structure.

Related literature

For related structures, see: Naicker et al. (2009 ▶, 2010 ▶); Alberach et al. (2004 ▶). For the synthesis of the title compound, see: Aubry et al. (2006 ▶).

Experimental

Crystal data

C20H23NO5

M = 357.39

Orthorhombic,

a = 5.3719 (7) Å

b = 12.1726 (14) Å

c = 27.021 (3) Å

V = 1766.9 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 173 K

0.20 × 0.12 × 0.12 mm

Data collection

Bruker Kappa DUO APEXII diffractometer

13619 measured reflections

2878 independent reflections

2538 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.090

S = 1.04

2878 reflections

239 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.26 e Å−3

Δρmin = −0.18 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; 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/S1600536810044909/hg2711sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810044909/hg2711Isup2.hkl

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

C20H23NO5	F(000) = 760
Mr = 357.39	Dx = 1.344 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 13619 reflections
a = 5.3719 (7) Å	θ = 2.3–29.6°
b = 12.1726 (14) Å	µ = 0.10 mm−1
c = 27.021 (3) Å	T = 173 K
V = 1766.9 (4) Å3	Needle, colourless
Z = 4	0.20 × 0.12 × 0.12 mm

Bruker Kappa DUO APEXII diffractometer	2538 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.032
graphite	θmax = 29.6°, θmin = 2.3°
0.5° φ scans and ω scans	h = −7→7
13619 measured reflections	k = −16→16
2878 independent reflections	l = −26→37

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0435P)2 + 0.3587P] where P = (Fo2 + 2Fc2)/3
2878 reflections	(Δ/σ)max = 0.001
239 parameters	Δρmax = 0.26 e Å−3
1 restraint	Δρmin = −0.18 e Å−3

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
C1	0.3734 (3)	0.44954 (13)	0.76583 (6)	0.0498 (4)
H1A	0.2473 (3)	0.28121 (11)	0.78678 (5)	0.0378 (3)
H1B	0.4011 (3)	0.34146 (11)	1.09674 (5)	0.0307 (3)
C2	0.3315 (3)	0.91415 (10)	0.85890 (5)	0.0351 (3)
H2	0.6521 (3)	0.82927 (10)	0.91879 (5)	0.0334 (3)
C4	0.0808 (3)	0.40422 (12)	0.87542 (5)	0.0253 (3)
H4	0.078 (4)	0.3258 (5)	0.8806 (7)	0.031 (5)*
C5	−0.0280 (3)	0.55050 (15)	0.81826 (7)	0.0269 (4)
C6	−0.0184	0.5713	0.7829	0.032*
H6	−0.1997	0.5652	0.8298	0.032*
C7	0.0265 (3)	0.42813 (14)	0.82338 (6)	0.0264 (4)
C8	−0.1279	0.3871	0.8141	0.032*
C9	0.3147 (3)	0.45361 (13)	0.89317 (6)	0.0224 (3)
H9	0.4574	0.4190	0.8752	0.027*
C10	0.3126 (3)	0.57639 (13)	0.88213 (6)	0.0211 (3)
C11	0.4841 (3)	0.64470 (14)	0.90671 (6)	0.0229 (3)
C12	0.5967	0.6136	0.9299	0.027*
H12A	0.4912 (3)	0.75648 (14)	0.89759 (6)	0.0242 (3)
H12B	0.3187 (4)	0.80245 (13)	0.86413 (6)	0.0250 (3)
H12C	0.1543 (3)	0.73469 (14)	0.83937 (6)	0.0253 (3)
C13	0.0407	0.7657	0.8164	0.030*
C14	0.1519 (3)	0.62062 (14)	0.84759 (6)	0.0231 (3)
H14	0.2348 (4)	0.39131 (15)	0.78851 (6)	0.0276 (4)
C15	0.4358 (4)	0.23681 (18)	0.75419 (8)	0.0383 (5)
H15	0.4304	0.1564	0.7553	0.057*
C16	0.6003	0.2623	0.7649	0.057*
C17	0.4044	0.2617	0.7203	0.057*
H17	0.3392 (3)	0.42874 (12)	0.94812 (6)	0.0216 (3)
C18	0.5433 (3)	0.37117 (13)	0.96620 (6)	0.0239 (3)
H18	0.6727	0.3501	0.9442	0.029*
C19	0.5606 (3)	0.34403 (14)	1.01604 (7)	0.0256 (3)
H19A	0.7007	0.3045	1.0280	0.031*
H19B	0.3716 (3)	0.37499 (13)	1.04827 (6)	0.0238 (3)
H19C	0.1682 (3)	0.43478 (13)	1.03116 (6)	0.0250 (3)
C20	0.0406	0.4574	1.0533	0.030*
H20A	0.1551 (3)	0.46090 (13)	0.98113 (6)	0.0245 (3)
H20B	0.0167	0.5017	0.9692	0.029*
H20C	0.1949 (4)	0.35863 (18)	1.12932 (7)	0.0399 (5)
C21	0.2374	0.3319	1.1625	0.060*
H21A	0.0496	0.3185	1.1169	0.060*
H21B	0.1564	0.4372	1.1309	0.060*
H21C	0.8323 (4)	0.78695 (16)	0.95244 (7)	0.0317 (4)
N1	0.9353	0.8473	0.9650	0.047*
H1N	0.9380	0.7335	0.9353	0.047*
O1	0.7474	0.7510	0.9802	0.047*
O2	0.1569 (4)	0.96322 (17)	0.82600 (8)	0.0419 (5)
O3	0.1835	1.0429	0.8252	0.063*
O4	−0.0125	0.9477	0.8375	0.063*
O5	0.1797	0.9329	0.7927	0.063*

	U11	U22	U33	U12	U13	U23
C1	0.0537 (10)	0.0375 (8)	0.0581 (10)	−0.0089 (8)	0.0274 (9)	−0.0036 (7)
H1A	0.0463 (8)	0.0301 (7)	0.0370 (7)	−0.0025 (6)	0.0121 (7)	−0.0065 (6)
H1B	0.0360 (7)	0.0309 (6)	0.0252 (6)	0.0054 (6)	0.0012 (5)	0.0018 (5)
C2	0.0433 (8)	0.0212 (6)	0.0409 (8)	−0.0014 (6)	−0.0095 (7)	0.0042 (5)
H2	0.0349 (7)	0.0253 (6)	0.0399 (7)	−0.0042 (6)	−0.0127 (6)	−0.0019 (5)
C4	0.0265 (7)	0.0241 (7)	0.0253 (7)	−0.0065 (6)	0.0018 (6)	−0.0012 (6)
C5	0.0242 (8)	0.0296 (8)	0.0269 (8)	−0.0021 (7)	−0.0041 (7)	−0.0024 (7)
C7	0.0256 (8)	0.0276 (8)	0.0261 (8)	−0.0063 (7)	0.0012 (7)	−0.0034 (7)
C9	0.0226 (7)	0.0205 (7)	0.0242 (7)	−0.0020 (6)	0.0033 (6)	−0.0014 (6)
C10	0.0214 (7)	0.0201 (7)	0.0218 (7)	−0.0015 (6)	0.0032 (6)	−0.0004 (6)
C11	0.0221 (7)	0.0237 (7)	0.0229 (7)	0.0002 (6)	−0.0005 (6)	0.0009 (6)
H12A	0.0246 (8)	0.0236 (7)	0.0246 (8)	−0.0022 (7)	−0.0007 (7)	−0.0023 (6)
H12B	0.0292 (8)	0.0207 (7)	0.0252 (8)	−0.0003 (7)	0.0020 (7)	0.0014 (6)
H12C	0.0256 (8)	0.0268 (8)	0.0235 (8)	0.0008 (7)	−0.0023 (7)	0.0023 (6)
C14	0.0229 (7)	0.0254 (7)	0.0211 (7)	−0.0019 (7)	0.0015 (7)	−0.0027 (6)
H14	0.0302 (9)	0.0302 (9)	0.0223 (8)	−0.0047 (7)	−0.0004 (7)	−0.0057 (7)
C15	0.0400 (11)	0.0407 (11)	0.0342 (10)	0.0036 (9)	0.0033 (9)	−0.0115 (9)
H17	0.0226 (7)	0.0175 (7)	0.0248 (8)	−0.0022 (6)	0.0006 (7)	−0.0006 (6)
C18	0.0198 (7)	0.0214 (7)	0.0304 (8)	0.0000 (6)	0.0042 (7)	−0.0027 (6)
C19	0.0214 (7)	0.0225 (7)	0.0329 (9)	0.0021 (6)	−0.0017 (7)	0.0004 (7)
H19B	0.0281 (8)	0.0185 (7)	0.0247 (8)	−0.0027 (6)	−0.0004 (7)	−0.0006 (6)
H19C	0.0252 (7)	0.0220 (7)	0.0278 (8)	0.0027 (7)	0.0041 (7)	−0.0028 (6)
H20A	0.0235 (7)	0.0211 (7)	0.0289 (8)	0.0036 (7)	0.0012 (7)	0.0006 (6)
H20C	0.0469 (12)	0.0432 (11)	0.0296 (9)	0.0033 (10)	0.0082 (9)	0.0042 (8)
H21C	0.0302 (9)	0.0348 (9)	0.0300 (9)	−0.0043 (8)	−0.0062 (8)	−0.0030 (7)
O2	0.0488 (12)	0.0272 (9)	0.0498 (12)	0.0069 (10)	−0.0084 (11)	0.0058 (8)

C1—H14	1.197 (2)	H12B—H12C	1.381 (2)
H1A—H14	1.343 (2)	H12C—C13	0.9500
H1A—C15	1.446 (2)	H12C—C14	1.406 (2)
H1B—H19B	1.381 (2)	C15—H15	0.9800
H1B—H20C	1.430 (2)	C15—C16	0.9800
C2—H12B	1.369 (2)	C15—C17	0.9800
C2—O2	1.424 (2)	H17—C18	1.390 (2)
H2—H12A	1.364 (2)	H17—H20A	1.388 (2)
H2—H21C	1.425 (2)	C18—H18	0.9500
C4—H4	0.965 (5)	C18—C19	1.390 (2)
C4—C7	1.465 (2)	C19—H19A	0.9500
C4—C9	1.473 (2)	C19—H19B	1.390 (2)
C5—C6	0.9900	H19B—H19C	1.392 (2)
C5—H6	0.9900	H19C—C20	0.9500
C5—C7	1.524 (3)	H19C—H20A	1.391 (2)
C5—C14	1.514 (2)	H20A—H20B	0.9500
C7—C8	1.0000	H20C—C21	0.9800
C7—H14	1.530 (3)	H20C—H21A	0.9800
C9—H9	1.0000	H20C—H21B	0.9800
C9—C10	1.524 (2)	H21C—N1	0.9800
C9—H17	1.521 (2)	H21C—H1N	0.9800
C10—C11	1.407 (2)	H21C—O1	0.9800
C10—C14	1.381 (2)	O2—O3	0.9800
C11—C12	0.9500	O2—O4	0.9800
C11—H12A	1.383 (2)	O2—O5	0.9800
H12A—H12B	1.410 (2)
C1—H14—H1A	122.83 (18)	H12B—C2—O2	116.62 (16)
C1—H14—C7	126.64 (17)	H12B—H12C—C13	119.4
H1A—H14—C7	110.53 (15)	H12B—H12C—C14	121.27 (16)
H1A—C15—H15	109.5	H12C—H12B—H12A	119.57 (15)
H1A—C15—C16	109.5	H12C—C14—C5	118.69 (16)
H1A—C15—C17	109.5	C14—C5—C6	109.1
H1B—H19B—C19	115.50 (16)	C14—C5—H6	109.1
H1B—H19B—H19C	124.03 (16)	C14—C5—C7	112.38 (15)
H1B—H20C—C21	109.5	C14—C10—C9	121.29 (15)
H1B—H20C—H21A	109.5	C14—C10—C11	119.86 (15)
H1B—H20C—H21B	109.5	C14—H12C—C13	119.4
C2—H12B—H12A	115.30 (16)	H14—H1A—C15	115.43 (16)
C2—H12B—H12C	125.13 (16)	H14—C7—C8	107.8
C2—O2—O3	109.5	H15—C15—C16	109.5
C2—O2—O4	109.5	H15—C15—C17	109.5
C2—O2—O5	109.5	C16—C15—C17	109.5
H2—H12A—C11	125.56 (16)	H17—C9—H9	108.9
H2—H12A—H12B	115.32 (15)	H17—C9—C10	112.76 (13)
H2—H21C—N1	109.5	H17—C18—H18	119.6
H2—H21C—H1N	109.5	H17—H20A—H19C	121.60 (16)
H2—H21C—O1	109.5	H17—H20A—H20B	119.2
C4—C7—C5	108.63 (14)	C18—H17—C9	120.77 (15)
C4—C7—C8	107.8	C18—C19—H19A	120.2
C4—C7—H14	112.79 (15)	C19—C18—H17	120.87 (16)
C4—C9—H9	108.9	C19—C18—H18	119.6
C4—C9—C10	109.28 (14)	C19—H19B—H19C	120.46 (16)
C4—C9—H17	108.07 (13)	H19B—H1B—H20C	116.85 (15)
C5—C7—C8	107.8	H19B—C19—C18	119.62 (16)
C5—C7—H14	111.78 (15)	H19B—C19—H19A	120.2
C6—C5—H6	107.9	H19B—H19C—C20	120.6
C7—C4—H4	109.5 (12)	H19C—H20A—H20B	119.2
C7—C4—C9	113.65 (13)	H20A—H17—C9	120.63 (15)
C7—C5—C6	109.1	H20A—H17—C18	118.58 (15)
C7—C5—H6	109.1	H20A—H19C—H19B	118.84 (16)
C9—C4—H4	111.7 (13)	H20A—H19C—C20	120.6
C10—C9—H9	108.9	C21—H20C—H21A	109.5
C10—C11—C12	119.5	C21—H20C—H21B	109.5
C10—C14—C5	122.23 (15)	H21A—H20C—H21B	109.5
C10—C14—H12C	119.08 (16)	N1—H21C—H1N	109.5
C11—C10—C9	118.82 (15)	N1—H21C—O1	109.5
C11—H12A—H12B	119.11 (16)	H1N—H21C—O1	109.5
H12A—H2—H21C	117.63 (14)	O3—O2—O4	109.5
H12A—C11—C10	121.00 (16)	O3—O2—O5	109.5
H12A—C11—C12	119.5	O4—O2—O5	109.5
H1B—H19B—H19C—H20A	−177.95 (16)	C11—C10—C14—C5	177.06 (15)
C2—H12B—H12C—C14	−179.09 (17)	C11—C10—C14—H12C	−3.2 (2)
H2—H12A—H12B—C2	−2.1 (2)	C11—H12A—H12B—C2	177.27 (16)
H2—H12A—H12B—H12C	177.55 (16)	C11—H12A—H12B—H12C	−3.1 (3)
C4—C7—H14—C1	−110.1 (2)	H12A—H12B—H12C—C14	1.3 (3)
C4—C7—H14—H1A	68.92 (19)	H12B—H12C—C14—C5	−178.36 (16)
C4—C9—C10—C11	163.71 (14)	H12B—H12C—C14—C10	1.9 (3)
C4—C9—C10—C14	−18.3 (2)	C14—C5—C7—C4	43.2 (2)
C4—C9—H17—C18	121.18 (16)	C14—C5—C7—H14	−81.93 (18)
C4—C9—H17—H20A	−57.33 (19)	C14—C10—C11—H12A	1.4 (2)
C5—C7—H14—C1	12.7 (3)	C15—H1A—H14—C1	−1.9 (3)
C5—C7—H14—H1A	−168.34 (16)	C15—H1A—H14—C7	179.03 (15)
C7—C4—C9—C10	53.33 (17)	H17—C9—C10—C11	43.5 (2)
C7—C4—C9—H17	176.36 (14)	H17—C9—C10—C14	−138.55 (16)
C7—C5—C14—C10	−11.8 (2)	H17—C18—C19—H19B	−0.1 (3)
C7—C5—C14—H12C	168.42 (16)	C18—H17—H20A—H19C	−1.4 (2)
C9—C4—C7—C5	−67.42 (18)	C18—C19—H19B—H1B	178.05 (15)
C9—C4—C7—H14	57.07 (19)	C18—C19—H19B—H19C	−1.3 (2)
C9—C10—C11—H12A	179.36 (15)	C19—H19B—H19C—H20A	1.3 (2)
C9—C10—C14—C5	−0.9 (2)	H19B—H19C—H20A—H17	0.0 (3)
C9—C10—C14—H12C	178.92 (15)	H20A—H17—C18—C19	1.5 (2)
C9—H17—C18—C19	−177.06 (15)	H20C—H1B—H19B—C19	−171.63 (16)
C9—H17—H20A—H19C	177.10 (15)	H20C—H1B—H19B—H19C	7.7 (2)
C10—C9—H17—C18	−117.93 (17)	H21C—H2—H12A—C11	1.4 (3)
C10—C9—H17—H20A	63.6 (2)	H21C—H2—H12A—H12B	−179.25 (15)
C10—C11—H12A—H2	−178.92 (16)	O2—C2—H12B—H12A	−178.97 (16)
C10—C11—H12A—H12B	1.8 (3)	O2—C2—H12B—H12C	1.4 (3)