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Geometric parameters of the title compound, C10H14NO2+·­Cl·H2O, are in the usual ranges. The tetra­hydro­pyridine ring adopts a half-chair conformation with the methyl group in an equatorial and the hydr­oxy group in an axial position. The crystal packing is stabilized by O—H...O, O—H...Cl and N—H...Cl hydrogen bonds. The absolute configurations of both chiral centres have been determined to be R.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807022003/pv2011sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807022003/pv2011Isup2.hkl
Contains datablock I

CCDC reference: 651422

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](Wave) = 0.000 Å
  • R factor = 0.030
  • wR factor = 0.079
  • Data-to-parameter ratio = 16.4

checkCIF/PLATON results

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Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.54 From the CIF: _reflns_number_total 2586 Count of symmetry unique reflns 1536 Completeness (_total/calc) 168.36% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1050 Fraction of Friedel pairs measured 0.684 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Synthesis of hydroxyl containing derivatives of tetrahydroisoquinolines are of interest as potential biologically active and medicinal substances. Aminoalkylamino derivatives of dihydroxy-benzoisoquinoline dione and of trihydroxy-naphtho[2,3-g]isoquinoline dione are biologically interesting molecules and synthesis and anti-tumor evaluation of these compounds are reported. 2-(Aminobenzyl)-1,2,3,4-tetrahydroisoquinolines are a new class of α2-adrenergic receptor antagonists. A new derivative of tetrahydroderivative of isoquinoline hydrochloride, C10H14NO2+Cl-.H2O, was prepared and its crystal structure was determined. Geometric parameters of the title compound are in the usual ranges. The tetrahydropyridine ring adopts a half chair conformation with the methyl group in an equatorial and the hydroxy group in an axial position. The crystal packing is stabilized by OH···O, OH···Cl and NH···Cl hydrogen bonds.

Related literature top

For related literature, see: Ammon & Wheeler (1974), Ribár et al. (1991), Kametani & Fukumoto (1975), Croisy-Delcey et al. (1988) and Stambach et al. (1993).

Experimental top

L-Phenylephrine.hydrochloride (10 g, 0.05 mol) was taken in 25 ml of water and stirred for 10 min. by adjusting the pH to 7 using 1 N sodium bicarbonate solution. 4 g of formaldehyde was added yo the above mixture and stirred for 3 days. The reaction mass was concentrated to residue. Acetone/ethylacetate mixture was added and filtered. The filtrate was allowed to evaporate. The crystals were obtained from a 1:1 mixture of acetone and toluene (m.p.: 507–509 K).

Refinement top

H atoms were found in a difference map, but those bonded to C were refined using a riding model with C—H ranging from 0.95Å to 1.00Å and Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(Cmethyl). The methyl group was allowed to rotate but not to tip. H atoms bonded to N and O were freely refined.

Structure description top

Synthesis of hydroxyl containing derivatives of tetrahydroisoquinolines are of interest as potential biologically active and medicinal substances. Aminoalkylamino derivatives of dihydroxy-benzoisoquinoline dione and of trihydroxy-naphtho[2,3-g]isoquinoline dione are biologically interesting molecules and synthesis and anti-tumor evaluation of these compounds are reported. 2-(Aminobenzyl)-1,2,3,4-tetrahydroisoquinolines are a new class of α2-adrenergic receptor antagonists. A new derivative of tetrahydroderivative of isoquinoline hydrochloride, C10H14NO2+Cl-.H2O, was prepared and its crystal structure was determined. Geometric parameters of the title compound are in the usual ranges. The tetrahydropyridine ring adopts a half chair conformation with the methyl group in an equatorial and the hydroxy group in an axial position. The crystal packing is stabilized by OH···O, OH···Cl and NH···Cl hydrogen bonds.

For related literature, see: Ammon & Wheeler (1974), Ribár et al. (1991), Kametani & Fukumoto (1975), Croisy-Delcey et al. (1988) and Stambach et al. (1993).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Perspective view of the title compound with the atom numbering; displacement ellipsoids are at the 50% probability level.
4,8-Dihydroxy-2-methyl-1,2,3,4-tetrahydroisoquinolinium chloride monohydrate top
Crystal data top
C10H14NO2+·Cl·H2OF(000) = 496
Mr = 233.69Dx = 1.371 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 5354 reflections
a = 7.3919 (7) Åθ = 3.1–27.2°
b = 7.4823 (7) ŵ = 0.33 mm1
c = 20.4655 (17) ÅT = 173 K
V = 1131.91 (18) Å3Block, colourless
Z = 40.49 × 0.48 × 0.45 mm
Data collection top
Stoe IPDSII two-circle
diffractometer
2586 independent reflections
Radiation source: fine-focus sealed tube2490 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
ω scansθmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan
(MULABS; Spek, 2003; Blessing, 1995)
h = 98
Tmin = 0.857, Tmax = 0.868k = 99
6824 measured reflectionsl = 2026
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.030 w = 1/[σ2(Fo2) + (0.0479P)2 + 0.1411P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.079(Δ/σ)max < 0.001
S = 1.07Δρmax = 0.23 e Å3
2586 reflectionsΔρmin = 0.18 e Å3
158 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.068 (5)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1057 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.02 (6)
Crystal data top
C10H14NO2+·Cl·H2OV = 1131.91 (18) Å3
Mr = 233.69Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.3919 (7) ŵ = 0.33 mm1
b = 7.4823 (7) ÅT = 173 K
c = 20.4655 (17) Å0.49 × 0.48 × 0.45 mm
Data collection top
Stoe IPDSII two-circle
diffractometer
2586 independent reflections
Absorption correction: multi-scan
(MULABS; Spek, 2003; Blessing, 1995)
2490 reflections with I > 2σ(I)
Tmin = 0.857, Tmax = 0.868Rint = 0.042
6824 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.079Δρmax = 0.23 e Å3
S = 1.07Δρmin = 0.18 e Å3
2586 reflectionsAbsolute structure: Flack (1983), 1057 Friedel pairs
158 parametersAbsolute structure parameter: 0.02 (6)
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.27972 (17)0.63969 (16)0.34303 (6)0.0225 (3)
H10.306 (3)0.526 (3)0.3266 (10)0.031 (5)*
C20.4382 (2)0.7638 (2)0.34089 (7)0.0252 (3)
H2A0.41210.87190.36720.030*
H2B0.46110.80150.29530.030*
C30.6041 (2)0.66956 (18)0.36796 (7)0.0225 (3)
H30.70300.75920.37410.027*
C40.5654 (2)0.57941 (19)0.43313 (7)0.0219 (3)
C50.3868 (2)0.55552 (18)0.45376 (7)0.0213 (3)
C60.2252 (2)0.60402 (19)0.41250 (7)0.0223 (3)
H6A0.13650.50500.41360.027*
H6B0.16630.71170.43080.027*
C70.3526 (2)0.47986 (19)0.51550 (7)0.0230 (3)
C80.4951 (2)0.4193 (2)0.55410 (8)0.0264 (3)
H80.47190.36630.59540.032*
C90.6720 (2)0.4370 (2)0.53162 (7)0.0267 (3)
H90.76910.39240.55730.032*
C100.7083 (2)0.5193 (2)0.47190 (7)0.0259 (3)
H100.82970.53430.45770.031*
C110.1222 (2)0.7095 (2)0.30450 (8)0.0329 (3)
H11A0.01830.62970.31030.049*
H11B0.15470.71480.25810.049*
H11C0.09080.82950.31990.049*
O310.66470 (15)0.53406 (15)0.32328 (6)0.0266 (3)
H310.689 (3)0.585 (3)0.2903 (11)0.036 (6)*
O710.17572 (16)0.46923 (16)0.53358 (6)0.0288 (3)
H710.164 (4)0.416 (3)0.5726 (14)0.055 (7)*
Cl10.23462 (5)0.24143 (5)0.300840 (16)0.02720 (12)
O1W0.13199 (19)0.32949 (16)0.65313 (6)0.0327 (3)
H1WA0.158 (4)0.215 (3)0.6527 (12)0.048 (6)*
H1WB0.014 (4)0.328 (4)0.6626 (13)0.059 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0220 (6)0.0246 (6)0.0208 (6)0.0007 (5)0.0004 (5)0.0000 (4)
C20.0270 (7)0.0229 (6)0.0258 (6)0.0009 (6)0.0040 (5)0.0023 (6)
C30.0227 (7)0.0214 (6)0.0235 (7)0.0017 (6)0.0035 (6)0.0011 (5)
C40.0243 (7)0.0224 (6)0.0191 (6)0.0011 (5)0.0001 (5)0.0024 (5)
C50.0230 (7)0.0209 (6)0.0201 (6)0.0006 (6)0.0009 (5)0.0017 (5)
C60.0199 (6)0.0260 (6)0.0210 (6)0.0001 (5)0.0023 (5)0.0005 (5)
C70.0258 (7)0.0224 (6)0.0207 (6)0.0007 (5)0.0019 (6)0.0023 (5)
C80.0342 (8)0.0244 (7)0.0207 (6)0.0003 (6)0.0014 (6)0.0009 (5)
C90.0280 (7)0.0281 (7)0.0238 (7)0.0017 (6)0.0066 (6)0.0016 (6)
C100.0218 (7)0.0312 (7)0.0248 (7)0.0020 (6)0.0009 (6)0.0039 (6)
C110.0265 (7)0.0426 (8)0.0295 (7)0.0063 (6)0.0046 (6)0.0075 (7)
O310.0311 (6)0.0263 (5)0.0222 (5)0.0014 (5)0.0081 (5)0.0011 (4)
O710.0274 (6)0.0329 (6)0.0262 (5)0.0015 (5)0.0054 (5)0.0039 (5)
Cl10.02922 (18)0.02989 (18)0.02250 (17)0.00307 (15)0.00038 (13)0.00474 (13)
O1W0.0373 (7)0.0282 (6)0.0325 (6)0.0009 (5)0.0079 (5)0.0043 (5)
Geometric parameters (Å, º) top
N1—C21.4957 (19)C6—H6B0.9900
N1—C111.500 (2)C7—O711.3611 (19)
N1—C61.5017 (18)C7—C81.393 (2)
N1—H10.94 (2)C8—C91.392 (2)
C2—C31.519 (2)C8—H80.9500
C2—H2A0.9900C9—C101.395 (2)
C2—H2B0.9900C9—H90.9500
C3—O311.4369 (18)C10—H100.9500
C3—C41.5218 (19)C11—H11A0.9800
C3—H31.0000C11—H11B0.9800
C4—C101.396 (2)C11—H11C0.9800
C4—C51.398 (2)O31—H310.79 (2)
C5—C71.407 (2)O71—H710.90 (3)
C5—C61.507 (2)O1W—H1WA0.88 (3)
C6—H6A0.9900O1W—H1WB0.89 (3)
C2—N1—C11112.12 (12)C5—C6—H6A109.4
C2—N1—C6110.38 (11)N1—C6—H6B109.4
C11—N1—C6110.57 (12)C5—C6—H6B109.4
C2—N1—H1113.3 (13)H6A—C6—H6B108.0
C11—N1—H1106.7 (13)O71—C7—C8123.60 (14)
C6—N1—H1103.4 (12)O71—C7—C5116.10 (14)
N1—C2—C3109.47 (11)C8—C7—C5120.29 (14)
N1—C2—H2A109.8C9—C8—C7119.47 (14)
C3—C2—H2A109.8C9—C8—H8120.3
N1—C2—H2B109.8C7—C8—H8120.3
C3—C2—H2B109.8C8—C9—C10120.83 (14)
H2A—C2—H2B108.2C8—C9—H9119.6
O31—C3—C2110.32 (12)C10—C9—H9119.6
O31—C3—C4107.67 (11)C9—C10—C4119.65 (14)
C2—C3—C4111.96 (12)C9—C10—H10120.2
O31—C3—H3108.9C4—C10—H10120.2
C2—C3—H3108.9N1—C11—H11A109.5
C4—C3—H3108.9N1—C11—H11B109.5
C10—C4—C5120.15 (13)H11A—C11—H11B109.5
C10—C4—C3119.93 (13)N1—C11—H11C109.5
C5—C4—C3119.92 (13)H11A—C11—H11C109.5
C4—C5—C7119.48 (13)H11B—C11—H11C109.5
C4—C5—C6123.27 (12)C3—O31—H31105.8 (16)
C7—C5—C6117.24 (13)C7—O71—H71111.2 (18)
N1—C6—C5111.15 (12)H1WA—O1W—H1WB102 (3)
N1—C6—H6A109.4
C11—N1—C2—C3167.99 (12)C11—N1—C6—C5173.04 (12)
C6—N1—C2—C368.26 (15)C4—C5—C6—N112.93 (18)
N1—C2—C3—O3170.79 (15)C7—C5—C6—N1165.99 (12)
N1—C2—C3—C449.10 (16)C4—C5—C7—O71176.75 (13)
O31—C3—C4—C1072.13 (16)C6—C5—C7—O714.29 (19)
C2—C3—C4—C10166.44 (13)C4—C5—C7—C83.9 (2)
O31—C3—C4—C5107.27 (15)C6—C5—C7—C8175.06 (13)
C2—C3—C4—C514.16 (18)O71—C7—C8—C9179.57 (15)
C10—C4—C5—C73.7 (2)C5—C7—C8—C91.1 (2)
C3—C4—C5—C7176.94 (12)C7—C8—C9—C101.9 (2)
C10—C4—C5—C6175.23 (14)C8—C9—C10—C42.1 (2)
C3—C4—C5—C64.2 (2)C5—C4—C10—C90.7 (2)
C2—N1—C6—C548.40 (15)C3—C4—C10—C9179.92 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O31i0.88 (3)1.93 (3)2.7733 (17)161 (2)
N1—H1···Cl10.94 (2)2.25 (2)3.1204 (13)153.6 (17)
O31—H31···Cl1ii0.79 (2)2.28 (2)3.0682 (12)177 (2)
O71—H71···O1W0.90 (3)1.79 (3)2.6803 (17)174 (2)
O1W—H1WB···Cl1i0.89 (3)2.26 (3)3.1299 (14)165 (3)
Symmetry codes: (i) x1/2, y+1/2, z+1; (ii) x+1, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC10H14NO2+·Cl·H2O
Mr233.69
Crystal system, space groupOrthorhombic, P212121
Temperature (K)173
a, b, c (Å)7.3919 (7), 7.4823 (7), 20.4655 (17)
V3)1131.91 (18)
Z4
Radiation typeMo Kα
µ (mm1)0.33
Crystal size (mm)0.49 × 0.48 × 0.45
Data collection
DiffractometerStoe IPDSII two-circle
Absorption correctionMulti-scan
(MULABS; Spek, 2003; Blessing, 1995)
Tmin, Tmax0.857, 0.868
No. of measured, independent and
observed [I > 2σ(I)] reflections
6824, 2586, 2490
Rint0.042
(sin θ/λ)max1)0.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.079, 1.07
No. of reflections2586
No. of parameters158
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.23, 0.18
Absolute structureFlack (1983), 1057 Friedel pairs
Absolute structure parameter0.02 (6)

Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O31i0.88 (3)1.93 (3)2.7733 (17)161 (2)
N1—H1···Cl10.94 (2)2.25 (2)3.1204 (13)153.6 (17)
O31—H31···Cl1ii0.79 (2)2.28 (2)3.0682 (12)177 (2)
O71—H71···O1W0.90 (3)1.79 (3)2.6803 (17)174 (2)
O1W—H1WB···Cl1i0.89 (3)2.26 (3)3.1299 (14)165 (3)
Symmetry codes: (i) x1/2, y+1/2, z+1; (ii) x+1, y+1/2, z+1/2.
 

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