(3S)-2-Benzyl-3-carb-oxy-1,2,3,4-tetra-hydro-isoquinolinium chloride monohydrate.

In the title compound, C(17)H(18)NO(2) (+)·Cl(-)·H(2)O, a precursor to novel asymmetric catalysts, the N-containing six-membered ring of the tetra-hydro-quinolinium unit assumes a half-boat conformation. In the crystal, inter-molecular O-H⋯O, O-H⋯Cl, N-H⋯Cl and C-H⋯O hydrogen bonds and C-H⋯π inter-actions link the mol-ecules into a three-dimensional network.

Related literature

For related structures of tetra­hydro­isoquinoline derivatives, see: Naicker, Petzold et al. (2010 ▶); Naicker, Govender et al. (2010 ▶, 2011 ▶); Peters et al. (2010 ▶). For related structures with the same chiral centre and conformation of the six-membered ring, see: Naicker et al. (2009 ▶); Chakka et al. (2010 ▶).

Experimental

Crystal data

C17H18NO2 +·Cl−·H2O

M = 321.79

Monoclinic,

a = 8.6159 (8) Å

b = 10.0670 (9) Å

c = 10.1392 (9) Å

β = 108.686 (2)°

V = 833.08 (13) Å3

Z = 2

Mo Kα radiation

μ = 0.24 mm−1

T = 193 K

0.30 × 0.11 × 0.02 mm

Data collection

Bruker Kappa DUO APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ▶) T min = 0.931, T max = 0.995

9083 measured reflections

4158 independent reflections

3414 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.082

S = 1.04

4158 reflections

213 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.19 e Å−3

Δρmin = −0.16 e Å−3

Absolute structure: Flack (1983 ▶), 1961 Friedel pairs

Flack parameter: −0.01 (5)

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810053122/is2635sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810053122/is2635Isup2.hkl

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

C17H18NO2+·Cl−·H2O	F(000) = 340
Mr = 321.79	Dx = 1.283 Mg m−3
Monoclinic, P21	Melting point: 479 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 8.6159 (8) Å	Cell parameters from 9083 reflections
b = 10.0670 (9) Å	θ = 2.1–28.3°
c = 10.1392 (9) Å	µ = 0.24 mm−1
β = 108.686 (2)°	T = 193 K
V = 833.08 (13) Å3	Needle, colourless
Z = 2	0.30 × 0.11 × 0.02 mm

Bruker Kappa DUO APEXII diffractometer	4158 independent reflections
Radiation source: fine-focus sealed tube	3414 reflections with I > 2σ(I)
graphite	Rint = 0.024
φ and ω scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a	h = −11→11
Tmin = 0.931, Tmax = 0.995	k = −13→13
9083 measured reflections	l = −13→13

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)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.082	w = 1/[σ2(Fo2) + (0.0365P)2 + 0.0675P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
4158 reflections	Δρmax = 0.19 e Å−3
213 parameters	Δρmin = −0.16 e Å−3
5 restraints	Absolute structure: Flack (1983), 1961 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.01 (5)

Experimental. Half sphere of data collected using the Bruker SAINT software package. Crystal to detector distance = 30 mm; combination of φ and ω scans of 0.5°, 30 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
Cl1	0.49392 (7)	0.38386 (5)	0.55522 (5)	0.04878 (14)
O1	0.52160 (16)	0.58413 (12)	−0.04364 (13)	0.0387 (3)
O2	0.6338 (2)	0.76556 (14)	−0.10233 (14)	0.0490 (4)
H2	0.629 (4)	0.716 (3)	−0.184 (2)	0.090 (9)*
O3	0.6423 (2)	0.66136 (15)	0.67265 (14)	0.0555 (4)
H3A	0.610 (3)	0.7278 (19)	0.601 (2)	0.067*
H3B	0.578 (3)	0.5841 (17)	0.634 (2)	0.067*
N1	0.49861 (17)	0.70659 (13)	0.19862 (14)	0.0280 (3)
H1	0.501 (2)	0.7664 (16)	0.2736 (15)	0.038 (5)*
C1	0.6027 (2)	0.59202 (17)	0.27205 (18)	0.0327 (4)
H1A	0.5619	0.5600	0.3472	0.039*
H1B	0.5925	0.5182	0.2052	0.039*
C2	0.7801 (2)	0.62971 (17)	0.33336 (17)	0.0310 (4)
C3	0.8823 (2)	0.5464 (2)	0.43363 (19)	0.0409 (5)
H3	0.8377	0.4710	0.4650	0.049*
C4	1.0477 (3)	0.5725 (2)	0.4878 (2)	0.0483 (5)
H4	1.1170	0.5144	0.5550	0.058*
C5	1.1130 (2)	0.6837 (2)	0.4441 (2)	0.0441 (5)
H5	1.2268	0.7026	0.4819	0.053*
C6	1.0113 (2)	0.7668 (2)	0.34518 (18)	0.0368 (4)
H6	1.0564	0.8426	0.3149	0.044*
C7	0.8446 (2)	0.74187 (16)	0.28922 (17)	0.0302 (4)
C8	0.7346 (2)	0.83776 (17)	0.18686 (17)	0.0305 (4)
H8A	0.7920	0.8686	0.1221	0.037*
H8B	0.7157	0.9162	0.2385	0.037*
C9	0.5689 (2)	0.77988 (16)	0.10185 (16)	0.0271 (3)
H9	0.4946	0.8568	0.0638	0.033*
C10	0.5722 (2)	0.69626 (16)	−0.02157 (17)	0.0292 (3)
C11	0.3223 (2)	0.66112 (18)	0.1368 (2)	0.0354 (4)
H11A	0.3204	0.5756	0.0880	0.043*
H11B	0.2765	0.6452	0.2133	0.043*
C12	0.2151 (2)	0.75869 (18)	0.03655 (19)	0.0343 (4)
C13	0.1818 (2)	0.8829 (2)	0.0808 (2)	0.0411 (4)
H13	0.2281	0.9074	0.1759	0.049*
C14	0.0813 (3)	0.9713 (2)	−0.0132 (3)	0.0522 (6)
H14	0.0603	1.0566	0.0173	0.063*
C15	0.0118 (3)	0.9354 (3)	−0.1511 (3)	0.0551 (6)
H15	−0.0581	0.9958	−0.2150	0.066*
C16	0.0432 (3)	0.8130 (2)	−0.1963 (2)	0.0512 (5)
H16	−0.0053	0.7886	−0.2911	0.061*
C17	0.1460 (2)	0.7249 (2)	−0.1032 (2)	0.0417 (4)
H17	0.1694	0.6408	−0.1351	0.050*

	U11	U22	U33	U12	U13	U23
Cl1	0.0783 (4)	0.0361 (2)	0.0339 (2)	−0.0070 (3)	0.0209 (2)	0.0013 (2)
O1	0.0530 (8)	0.0247 (6)	0.0402 (7)	−0.0058 (6)	0.0177 (6)	−0.0053 (6)
O2	0.0828 (11)	0.0376 (8)	0.0353 (7)	−0.0184 (7)	0.0311 (7)	−0.0053 (6)
O3	0.0928 (12)	0.0438 (9)	0.0322 (7)	−0.0064 (8)	0.0231 (8)	−0.0007 (7)
N1	0.0354 (7)	0.0231 (7)	0.0269 (7)	−0.0014 (6)	0.0120 (6)	0.0022 (6)
C1	0.0427 (10)	0.0236 (8)	0.0313 (9)	−0.0004 (7)	0.0111 (7)	0.0065 (7)
C2	0.0415 (10)	0.0274 (8)	0.0249 (8)	0.0019 (7)	0.0116 (7)	0.0006 (7)
C3	0.0514 (12)	0.0373 (10)	0.0329 (10)	0.0028 (9)	0.0121 (9)	0.0067 (8)
C4	0.0530 (13)	0.0483 (12)	0.0370 (10)	0.0094 (10)	0.0050 (9)	0.0085 (10)
C5	0.0384 (10)	0.0502 (12)	0.0391 (10)	0.0028 (9)	0.0061 (8)	−0.0071 (9)
C6	0.0408 (10)	0.0375 (10)	0.0324 (9)	−0.0053 (8)	0.0119 (8)	−0.0057 (8)
C7	0.0404 (9)	0.0276 (9)	0.0231 (8)	0.0001 (7)	0.0111 (7)	−0.0032 (7)
C8	0.0379 (9)	0.0232 (8)	0.0293 (8)	−0.0051 (7)	0.0092 (7)	−0.0001 (7)
C9	0.0351 (9)	0.0181 (7)	0.0281 (8)	−0.0011 (7)	0.0100 (7)	0.0030 (7)
C10	0.0367 (9)	0.0223 (8)	0.0274 (8)	−0.0004 (7)	0.0086 (7)	0.0015 (7)
C11	0.0369 (10)	0.0309 (9)	0.0406 (10)	−0.0051 (8)	0.0154 (8)	0.0026 (8)
C12	0.0312 (9)	0.0319 (9)	0.0422 (9)	−0.0031 (7)	0.0150 (7)	0.0035 (8)
C13	0.0399 (10)	0.0397 (10)	0.0492 (10)	0.0035 (9)	0.0220 (8)	−0.0013 (11)
C14	0.0511 (13)	0.0396 (11)	0.0771 (16)	0.0143 (10)	0.0360 (12)	0.0076 (11)
C15	0.0482 (13)	0.0631 (15)	0.0600 (14)	0.0194 (11)	0.0256 (11)	0.0236 (12)
C16	0.0491 (12)	0.0586 (14)	0.0448 (12)	0.0056 (10)	0.0135 (10)	0.0106 (11)
C17	0.0430 (11)	0.0393 (11)	0.0428 (10)	−0.0021 (9)	0.0138 (9)	−0.0004 (9)

O1—C10	1.205 (2)	C6—H6	0.9500
O2—C10	1.310 (2)	C7—C8	1.509 (2)
O2—H2	0.961 (10)	C8—C9	1.527 (2)
O3—H3A	0.957 (10)	C8—H8A	0.9900
O3—H3B	0.963 (10)	C8—H8B	0.9900
N1—C9	1.502 (2)	C9—C10	1.516 (2)
N1—C1	1.504 (2)	C9—H9	1.0000
N1—C11	1.516 (2)	C11—C12	1.500 (3)
N1—H1	0.965 (9)	C11—H11A	0.9900
C1—C2	1.502 (3)	C11—H11B	0.9900
C1—H1A	0.9900	C12—C13	1.390 (3)
C1—H1B	0.9900	C12—C17	1.392 (3)
C2—C3	1.392 (2)	C13—C14	1.386 (3)
C2—C7	1.394 (2)	C13—H13	0.9500
C3—C4	1.379 (3)	C14—C15	1.382 (3)
C3—H3	0.9500	C14—H14	0.9500
C4—C5	1.388 (3)	C15—C16	1.371 (3)
C4—H4	0.9500	C15—H15	0.9500
C5—C6	1.382 (3)	C16—C17	1.388 (3)
C5—H5	0.9500	C16—H16	0.9500
C6—C7	1.388 (2)	C17—H17	0.9500
C10—O2—H2	110.4 (19)	C9—C8—H8B	108.7
H3A—O3—H3B	106 (2)	H8A—C8—H8B	107.6
C9—N1—C1	113.50 (13)	N1—C9—C10	112.63 (13)
C9—N1—C11	116.00 (13)	N1—C9—C8	108.58 (13)
C1—N1—C11	109.44 (13)	C10—C9—C8	114.61 (14)
C9—N1—H1	107.3 (12)	N1—C9—H9	106.9
C1—N1—H1	103.3 (12)	C10—C9—H9	106.9
C11—N1—H1	106.2 (11)	C8—C9—H9	106.9
C2—C1—N1	112.18 (13)	O1—C10—O2	125.28 (17)
C2—C1—H1A	109.2	O1—C10—C9	124.90 (16)
N1—C1—H1A	109.2	O2—C10—C9	109.79 (14)
C2—C1—H1B	109.2	C12—C11—N1	113.61 (14)
N1—C1—H1B	109.2	C12—C11—H11A	108.8
H1A—C1—H1B	107.9	N1—C11—H11A	108.8
C3—C2—C7	119.88 (17)	C12—C11—H11B	108.8
C3—C2—C1	118.13 (15)	N1—C11—H11B	108.8
C7—C2—C1	121.95 (15)	H11A—C11—H11B	107.7
C4—C3—C2	120.48 (18)	C13—C12—C17	118.93 (18)
C4—C3—H3	119.8	C13—C12—C11	121.11 (17)
C2—C3—H3	119.8	C17—C12—C11	119.95 (17)
C3—C4—C5	119.98 (18)	C14—C13—C12	120.24 (19)
C3—C4—H4	120.0	C14—C13—H13	119.9
C5—C4—H4	120.0	C12—C13—H13	119.9
C6—C5—C4	119.49 (18)	C15—C14—C13	120.1 (2)
C6—C5—H5	120.3	C15—C14—H14	120.0
C4—C5—H5	120.3	C13—C14—H14	120.0
C5—C6—C7	121.30 (18)	C16—C15—C14	120.3 (2)
C5—C6—H6	119.4	C16—C15—H15	119.8
C7—C6—H6	119.4	C14—C15—H15	119.8
C6—C7—C2	118.85 (16)	C15—C16—C17	119.9 (2)
C6—C7—C8	120.32 (15)	C15—C16—H16	120.0
C2—C7—C8	120.78 (16)	C17—C16—H16	120.0
C7—C8—C9	114.30 (14)	C16—C17—C12	120.5 (2)
C7—C8—H8A	108.7	C16—C17—H17	119.8
C9—C8—H8A	108.7	C12—C17—H17	119.8
C7—C8—H8B	108.7
C9—N1—C1—C2	47.47 (18)	C11—N1—C9—C8	170.53 (14)
C11—N1—C1—C2	178.80 (14)	C7—C8—C9—N1	46.10 (19)
N1—C1—C2—C3	163.47 (15)	C7—C8—C9—C10	−80.80 (18)
N1—C1—C2—C7	−18.8 (2)	N1—C9—C10—O1	1.5 (2)
C7—C2—C3—C4	−1.3 (3)	C8—C9—C10—O1	126.28 (19)
C1—C2—C3—C4	176.48 (18)	N1—C9—C10—O2	179.67 (14)
C2—C3—C4—C5	1.1 (3)	C8—C9—C10—O2	−55.54 (19)
C3—C4—C5—C6	−0.7 (3)	C9—N1—C11—C12	−37.9 (2)
C4—C5—C6—C7	0.5 (3)	C1—N1—C11—C12	−167.86 (14)
C5—C6—C7—C2	−0.7 (3)	N1—C11—C12—C13	−65.2 (2)
C5—C6—C7—C8	176.86 (17)	N1—C11—C12—C17	115.34 (18)
C3—C2—C7—C6	1.1 (2)	C17—C12—C13—C14	0.0 (3)
C1—C2—C7—C6	−176.63 (16)	C11—C12—C13—C14	−179.48 (18)
C3—C2—C7—C8	−176.46 (16)	C12—C13—C14—C15	1.0 (3)
C1—C2—C7—C8	5.9 (2)	C13—C14—C15—C16	−0.8 (3)
C6—C7—C8—C9	162.44 (15)	C14—C15—C16—C17	−0.3 (3)
C2—C7—C8—C9	−20.1 (2)	C15—C16—C17—C12	1.3 (3)
C1—N1—C9—C10	66.57 (17)	C13—C12—C17—C16	−1.1 (3)
C11—N1—C9—C10	−61.44 (18)	C11—C12—C17—C16	178.37 (18)
C1—N1—C9—C8	−61.46 (17)

Cg is the centroid of the C12–C17 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1i	0.97 (2)	2.09 (2)	3.0521 (15)	176.(1)
O2—H2···O3ii	0.96 (2)	1.59 (2)	2.533 (2)	167 (3)
O3—H3A···Cl1i	0.96 (2)	2.21 (2)	3.1615 (15)	172 (2)
O3—H3B···Cl1	0.96 (2)	2.20 (2)	3.1434 (16)	165 (2)
C9—H9···O1iii	1.00	2.30	3.169 (2)	145
C15—H15···Cgiii	0.95	2.78	3.386 (3)	122

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C12–C17 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl1i	0.97 (2)	2.09 (2)	3.0521 (15)	176 (1)
O2—H2⋯O3ii	0.96 (2)	1.59 (2)	2.533 (2)	167 (3)
O3—H3A⋯Cl1i	0.96 (2)	2.21 (2)	3.1615 (15)	172 (2)
O3—H3B⋯Cl1	0.96 (2)	2.20 (2)	3.1434 (16)	165 (2)
C9—H9⋯O1iii	1.00	2.30	3.169 (2)	145
C15—H15⋯Cgiii	0.95	2.78	3.386 (3)	122

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