[(1R,3S)-6,7-Dimeth-oxy-1-phenyl-1,2,3,4-tetra-hydro-isoquinolin-3-yl]methanol 2.33-hydrate.

The title compound, C(18)H(21)NO(3)·2.33H(2)O, is the fourth reported member in a series of (1R,3S)-6,7-dimeth-oxy-1-phenyl-1,2,3,4-tetra-hydro-isoquinoline derivatives used in catalysis as ligands (or their precursors). The N-heterocycle in the structure adopts a half-chair conformation. The dihedral angle between the benzene rings is 77.29 (13)°. There are three ill-resolved water molecules of crystallization in the structure (one of them rotationally disordered about a threefold axis) involved in short contacts probably due to hydrogen bonding.

Related literature

For the synthesis of the ligand, see: Chakka et al. (2009 ▶). For the Henry reaction, see: Kawthekar et al. (2010 ▶). For similar structures, see: Naicker et al. (2009 ▶, 2010a ▶,b ▶); Chakka et al. (2010 ▶).

Experimental

Crystal data

C18H21NO3·2.33H2O

M = 341.39

Trigonal,

a = 27.950 (2) Å

c = 5.8035 (5) Å

V = 3926 (2) Å3

Z = 9

Mo Kα radiation

μ = 0.10 mm−1

T = 173 K

0.13 × 0.12 × 0.09 mm

Data collection

Bruker Kappa DUO APEXII CCD diffractometer

10224 measured reflections

4340 independent reflections

3707 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.162

S = 1.06

4340 reflections

226 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.60 e Å−3

Δρmin = −0.30 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/S1600536811006052/bg2388sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811006052/bg2388Isup2.hkl

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

C18H21NO3·2.33H2O	Dx = 1.299 Mg m−3
Mr = 341.39	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 10224 reflections
Hall symbol: R 3	θ = 2.5–28.3°
a = 27.950 (2) Å	µ = 0.10 mm−1
c = 5.8035 (5) Å	T = 173 K
V = 3926 (2) Å3	Needle, colourless
Z = 9	0.13 × 0.12 × 0.09 mm
F(000) = 1650

Bruker Kappa DUO APEXII CCD diffractometer	3707 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.022
graphite	θmax = 28.3°, θmin = 2.5°
0.5° φ scans and ω	h = −37→37
10224 measured reflections	k = −31→37
4340 independent reflections	l = −7→7

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0985P)2 + 2.1271P] where P = (Fo2 + 2Fc2)/3
4340 reflections	(Δ/σ)max < 0.001
226 parameters	Δρmax = 0.60 e Å−3
3 restraints	Δρmin = −0.30 e Å−3

Experimental. Half sphere of data collected using SAINT strategy (Bruker, 2006). Crystal to detector distance = 50 mm; combination of φ and ω scans of 0.5°, 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	0.91196 (8)	0.15356 (9)	0.2897 (4)	0.0468 (5)
O2	0.95248 (8)	0.22297 (9)	0.6202 (3)	0.0484 (5)
O3	0.67745 (12)	0.27007 (15)	0.4378 (6)	0.0809 (9)
H3O	0.675 (2)	0.287 (2)	0.291 (5)	0.097*
O1W	0.6667	0.3333	0.0620 (11)	0.0959 (17)*
O2W	0.82161 (9)	0.36012 (8)	0.0053 (3)	0.0477 (5)
O3W	0.76609 (13)	0.41438 (12)	−0.0962 (6)	0.0806 (8)
N1	0.75539 (10)	0.24710 (8)	0.1792 (4)	0.0370 (5)
H1N	0.7216 (8)	0.2411 (13)	0.108 (5)	0.043*
C1	0.76741 (9)	0.20211 (9)	0.1292 (4)	0.0285 (4)
H1	0.7785	0.2059	−0.0366	0.034*
C2	0.81654 (9)	0.20906 (9)	0.2690 (4)	0.0299 (4)
C3	0.84111 (9)	0.17779 (10)	0.2090 (4)	0.0327 (5)
H3	0.8270	0.1529	0.0825	0.039*
C4	0.88544 (10)	0.18267 (10)	0.3311 (4)	0.0348 (5)
C5	0.90748 (11)	0.22030 (11)	0.5167 (4)	0.0369 (5)
C6	0.88280 (12)	0.25024 (10)	0.5776 (4)	0.0375 (5)
H6	0.8969	0.2749	0.7045	0.045*
C7	0.83662 (10)	0.24501 (9)	0.4548 (4)	0.0314 (5)
C8	0.81126 (12)	0.27861 (10)	0.5265 (4)	0.0399 (6)
H8A	0.8346	0.3171	0.4722	0.048*
H8B	0.8096	0.2793	0.6968	0.048*
C9	0.75403 (13)	0.25544 (11)	0.4300 (4)	0.0411 (6)
H9	0.7287	0.2193	0.5058	0.049*
C10	0.73288 (16)	0.29565 (15)	0.4714 (7)	0.0594 (8)
H10A	0.7417	0.3100	0.6310	0.071*
H10B	0.7516	0.3274	0.3646	0.071*
C11	0.71644 (9)	0.14513 (9)	0.1564 (4)	0.0280 (4)
C12	0.70780 (10)	0.11199 (10)	0.3506 (4)	0.0337 (5)
H12	0.7343	0.1252	0.4715	0.040*
C13	0.66148 (12)	0.06060 (11)	0.3683 (5)	0.0433 (6)
H13	0.6562	0.0387	0.5013	0.052*
C14	0.62243 (11)	0.04056 (11)	0.1934 (6)	0.0463 (7)
H14	0.5909	0.0047	0.2051	0.056*
C15	0.62937 (11)	0.07295 (11)	0.0015 (5)	0.0451 (6)
H15	0.6024	0.0597	−0.1175	0.054*
C16	0.67646 (10)	0.12540 (10)	−0.0156 (4)	0.0374 (5)
H16	0.6811	0.1478	−0.1464	0.045*
C17	0.88839 (12)	0.11055 (14)	0.1231 (6)	0.0509 (7)
H17A	0.9112	0.0931	0.1098	0.076*
H17B	0.8868	0.1260	−0.0264	0.076*
H17C	0.8510	0.0829	0.1711	0.076*
C18	0.97424 (13)	0.25805 (14)	0.8174 (5)	0.0533 (8)
H18A	1.0064	0.2566	0.8759	0.080*
H18B	0.9458	0.2455	0.9375	0.080*
H18C	0.9854	0.2961	0.7738	0.080*

	U11	U22	U33	U12	U13	U23
O1	0.0351 (10)	0.0572 (12)	0.0562 (11)	0.0292 (9)	−0.0095 (8)	−0.0163 (9)
O2	0.0420 (10)	0.0542 (12)	0.0480 (11)	0.0233 (9)	−0.0183 (8)	−0.0117 (9)
O3	0.0626 (17)	0.092 (2)	0.095 (2)	0.0430 (15)	−0.0005 (15)	−0.0043 (17)
O2W	0.0541 (12)	0.0409 (10)	0.0489 (11)	0.0243 (9)	0.0054 (9)	0.0036 (8)
O3W	0.0695 (17)	0.0625 (16)	0.115 (2)	0.0372 (14)	−0.0191 (16)	−0.0032 (15)
N1	0.0478 (12)	0.0286 (10)	0.0405 (11)	0.0235 (9)	−0.0004 (9)	0.0020 (8)
C1	0.0311 (11)	0.0278 (10)	0.0258 (9)	0.0141 (9)	0.0038 (8)	0.0054 (8)
C2	0.0331 (11)	0.0253 (10)	0.0273 (10)	0.0117 (9)	0.0072 (8)	0.0055 (8)
C3	0.0296 (11)	0.0341 (11)	0.0305 (11)	0.0130 (9)	0.0028 (8)	−0.0035 (8)
C4	0.0294 (11)	0.0373 (12)	0.0332 (11)	0.0131 (10)	0.0024 (9)	−0.0009 (9)
C5	0.0372 (12)	0.0357 (12)	0.0328 (11)	0.0143 (10)	−0.0036 (9)	0.0022 (9)
C6	0.0500 (14)	0.0312 (11)	0.0271 (10)	0.0170 (11)	−0.0019 (10)	−0.0004 (9)
C7	0.0410 (12)	0.0218 (10)	0.0298 (10)	0.0145 (9)	0.0017 (9)	0.0031 (8)
C8	0.0631 (17)	0.0325 (12)	0.0303 (11)	0.0284 (12)	−0.0007 (11)	−0.0016 (9)
C9	0.0557 (16)	0.0351 (12)	0.0414 (13)	0.0295 (12)	0.0118 (11)	0.0061 (10)
C10	0.063 (2)	0.0548 (18)	0.072 (2)	0.0387 (17)	0.0177 (16)	0.0012 (15)
C11	0.0309 (11)	0.0252 (10)	0.0307 (10)	0.0162 (9)	0.0070 (8)	0.0024 (8)
C12	0.0377 (12)	0.0328 (11)	0.0374 (12)	0.0227 (10)	0.0091 (9)	0.0091 (9)
C13	0.0474 (14)	0.0320 (12)	0.0557 (15)	0.0237 (11)	0.0239 (12)	0.0150 (11)
C14	0.0347 (13)	0.0298 (12)	0.0675 (18)	0.0108 (10)	0.0190 (13)	−0.0014 (11)
C15	0.0336 (12)	0.0370 (13)	0.0546 (16)	0.0101 (11)	0.0033 (11)	−0.0077 (11)
C16	0.0375 (12)	0.0350 (12)	0.0374 (12)	0.0165 (10)	0.0038 (10)	0.0016 (10)
C17	0.0382 (14)	0.0600 (17)	0.0640 (19)	0.0317 (14)	−0.0060 (12)	−0.0230 (14)
C18	0.0462 (16)	0.0548 (17)	0.0419 (14)	0.0126 (13)	−0.0158 (12)	−0.0037 (12)

O1—C4	1.368 (3)	C8—H8B	0.9900
O1—C17	1.422 (3)	C9—C10	1.528 (4)
O2—C5	1.362 (3)	C9—H9	1.0000
O2—C18	1.430 (3)	C10—H10A	0.9900
O3—C10	1.357 (5)	C10—H10B	0.9900
O3—H3O	0.99 (4)	C11—C16	1.390 (3)
N1—C9	1.477 (3)	C11—C12	1.401 (3)
N1—C1	1.484 (3)	C12—C13	1.375 (4)
N1—H1N	0.97 (3)	C12—H12	0.9500
C1—C2	1.521 (3)	C13—C14	1.387 (5)
C1—C11	1.524 (3)	C13—H13	0.9500
C1—H1	1.0000	C14—C15	1.386 (4)
C2—C7	1.387 (3)	C14—H14	0.9500
C2—C3	1.399 (3)	C15—C16	1.401 (4)
C3—C4	1.374 (3)	C15—H15	0.9500
C3—H3	0.9500	C16—H16	0.9500
C4—C5	1.414 (3)	C17—H17A	0.9800
C5—C6	1.370 (4)	C17—H17B	0.9800
C6—C7	1.417 (4)	C17—H17C	0.9800
C6—H6	0.9500	C18—H18A	0.9800
C7—C8	1.491 (3)	C18—H18B	0.9800
C8—C9	1.502 (4)	C18—H18C	0.9800
C8—H8A	0.9900
C4—O1—C17	117.5 (2)	N1—C9—H9	109.6
C5—O2—C18	117.1 (2)	C8—C9—H9	109.6
C10—O3—H3O	102 (3)	C10—C9—H9	109.6
C9—N1—C1	111.16 (18)	O3—C10—C9	110.5 (3)
C9—N1—H1N	110 (2)	O3—C10—H10A	109.6
C1—N1—H1N	112.6 (19)	C9—C10—H10A	109.6
N1—C1—C2	111.10 (19)	O3—C10—H10B	109.6
N1—C1—C11	112.09 (18)	C9—C10—H10B	109.6
C2—C1—C11	113.00 (17)	H10A—C10—H10B	108.1
N1—C1—H1	106.7	C16—C11—C12	118.5 (2)
C2—C1—H1	106.7	C16—C11—C1	119.09 (19)
C11—C1—H1	106.7	C12—C11—C1	122.4 (2)
C7—C2—C3	119.9 (2)	C13—C12—C11	120.8 (3)
C7—C2—C1	121.3 (2)	C13—C12—H12	119.6
C3—C2—C1	118.74 (19)	C11—C12—H12	119.6
C4—C3—C2	120.6 (2)	C12—C13—C14	120.5 (2)
C4—C3—H3	119.7	C12—C13—H13	119.8
C2—C3—H3	119.7	C14—C13—H13	119.8
O1—C4—C3	125.5 (2)	C15—C14—C13	120.0 (2)
O1—C4—C5	114.3 (2)	C15—C14—H14	120.0
C3—C4—C5	120.2 (2)	C13—C14—H14	120.0
O2—C5—C6	125.9 (2)	C14—C15—C16	119.5 (3)
O2—C5—C4	115.1 (2)	C14—C15—H15	120.3
C6—C5—C4	119.1 (2)	C16—C15—H15	120.3
C5—C6—C7	121.2 (2)	C11—C16—C15	120.8 (2)
C5—C6—H6	119.4	C11—C16—H16	119.6
C7—C6—H6	119.4	C15—C16—H16	119.6
C2—C7—C6	118.9 (2)	O1—C17—H17A	109.5
C2—C7—C8	121.7 (2)	O1—C17—H17B	109.5
C6—C7—C8	119.4 (2)	H17A—C17—H17B	109.5
C7—C8—C9	111.3 (2)	O1—C17—H17C	109.5
C7—C8—H8A	109.4	H17A—C17—H17C	109.5
C9—C8—H8A	109.4	H17B—C17—H17C	109.5
C7—C8—H8B	109.4	O2—C18—H18A	109.5
C9—C8—H8B	109.4	O2—C18—H18B	109.5
H8A—C8—H8B	108.0	H18A—C18—H18B	109.5
N1—C9—C8	109.2 (2)	O2—C18—H18C	109.5
N1—C9—C10	108.7 (2)	H18A—C18—H18C	109.5
C8—C9—C10	110.2 (2)	H18B—C18—H18C	109.5
C9—N1—C1—C2	−48.0 (3)	C1—C2—C7—C8	−0.1 (3)
C9—N1—C1—C11	79.5 (3)	C5—C6—C7—C2	−0.4 (3)
N1—C1—C2—C7	14.4 (3)	C5—C6—C7—C8	−179.7 (2)
C11—C1—C2—C7	−112.6 (2)	C2—C7—C8—C9	18.5 (3)
N1—C1—C2—C3	−166.43 (19)	C6—C7—C8—C9	−162.2 (2)
C11—C1—C2—C3	66.6 (3)	C1—N1—C9—C8	68.4 (2)
C7—C2—C3—C4	−0.6 (3)	C1—N1—C9—C10	−171.4 (2)
C1—C2—C3—C4	−179.8 (2)	C7—C8—C9—N1	−51.1 (3)
C17—O1—C4—C3	−7.1 (4)	C7—C8—C9—C10	−170.5 (2)
C17—O1—C4—C5	173.1 (3)	N1—C9—C10—O3	75.4 (3)
C2—C3—C4—O1	178.9 (2)	C8—C9—C10—O3	−165.0 (3)
C2—C3—C4—C5	−1.2 (4)	N1—C1—C11—C16	76.9 (3)
C18—O2—C5—C6	3.4 (4)	C2—C1—C11—C16	−156.7 (2)
C18—O2—C5—C4	−176.4 (2)	N1—C1—C11—C12	−102.1 (2)
O1—C4—C5—O2	2.0 (3)	C2—C1—C11—C12	24.3 (3)
C3—C4—C5—O2	−177.9 (2)	C16—C11—C12—C13	1.5 (3)
O1—C4—C5—C6	−177.9 (2)	C1—C11—C12—C13	−179.5 (2)
C3—C4—C5—C6	2.3 (4)	C11—C12—C13—C14	0.1 (4)
O2—C5—C6—C7	178.7 (2)	C12—C13—C14—C15	−1.5 (4)
C4—C5—C6—C7	−1.5 (4)	C13—C14—C15—C16	1.2 (4)
C3—C2—C7—C6	1.4 (3)	C12—C11—C16—C15	−1.8 (4)
C1—C2—C7—C6	−179.4 (2)	C1—C11—C16—C15	179.2 (2)
C3—C2—C7—C8	−179.2 (2)	C14—C15—C16—C11	0.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O1W	0.99 (4)	1.95 (4)	2.917 (6)	164 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯O1W	0.99 (4)	1.95 (4)	2.917 (6)	164 (5)