Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807022003/pv2011sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807022003/pv2011Isup2.hkl |
CCDC reference: 651422
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (Wave) = 0.000 Å
- R factor = 0.030
- wR factor = 0.079
- Data-to-parameter ratio = 16.4
checkCIF/PLATON results
No syntax errors found
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
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).
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.
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).
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.
Fig. 1. Perspective view of the title compound with the atom numbering; displacement ellipsoids are at the 50% probability level. |
C10H14NO2+·Cl−·H2O | F(000) = 496 |
Mr = 233.69 | Dx = 1.371 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 5354 reflections |
a = 7.3919 (7) Å | θ = 3.1–27.2° |
b = 7.4823 (7) Å | µ = 0.33 mm−1 |
c = 20.4655 (17) Å | T = 173 K |
V = 1131.91 (18) Å3 | Block, colourless |
Z = 4 | 0.49 × 0.48 × 0.45 mm |
Stoe IPDSII two-circle diffractometer | 2586 independent reflections |
Radiation source: fine-focus sealed tube | 2490 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
ω scans | θmax = 27.5°, θmin = 2.9° |
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | h = −9→8 |
Tmin = 0.857, Tmax = 0.868 | k = −9→9 |
6824 measured reflections | l = −20→26 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H 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 = 1.07 | Δρmax = 0.23 e Å−3 |
2586 reflections | Δρmin = −0.18 e Å−3 |
158 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.068 (5) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 1057 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.02 (6) |
C10H14NO2+·Cl−·H2O | V = 1131.91 (18) Å3 |
Mr = 233.69 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.3919 (7) Å | µ = 0.33 mm−1 |
b = 7.4823 (7) Å | T = 173 K |
c = 20.4655 (17) Å | 0.49 × 0.48 × 0.45 mm |
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 = 0.868 | Rint = 0.042 |
6824 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.079 | Δρmax = 0.23 e Å−3 |
S = 1.07 | Δρmin = −0.18 e Å−3 |
2586 reflections | Absolute structure: Flack (1983), 1057 Friedel pairs |
158 parameters | Absolute structure parameter: 0.02 (6) |
0 restraints |
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 | ||
N1 | 0.27972 (17) | 0.63969 (16) | 0.34303 (6) | 0.0225 (3) | |
H1 | 0.306 (3) | 0.526 (3) | 0.3266 (10) | 0.031 (5)* | |
C2 | 0.4382 (2) | 0.7638 (2) | 0.34089 (7) | 0.0252 (3) | |
H2A | 0.4121 | 0.8719 | 0.3672 | 0.030* | |
H2B | 0.4611 | 0.8015 | 0.2953 | 0.030* | |
C3 | 0.6041 (2) | 0.66956 (18) | 0.36796 (7) | 0.0225 (3) | |
H3 | 0.7030 | 0.7592 | 0.3741 | 0.027* | |
C4 | 0.5654 (2) | 0.57941 (19) | 0.43313 (7) | 0.0219 (3) | |
C5 | 0.3868 (2) | 0.55552 (18) | 0.45376 (7) | 0.0213 (3) | |
C6 | 0.2252 (2) | 0.60402 (19) | 0.41250 (7) | 0.0223 (3) | |
H6A | 0.1365 | 0.5050 | 0.4136 | 0.027* | |
H6B | 0.1663 | 0.7117 | 0.4308 | 0.027* | |
C7 | 0.3526 (2) | 0.47986 (19) | 0.51550 (7) | 0.0230 (3) | |
C8 | 0.4951 (2) | 0.4193 (2) | 0.55410 (8) | 0.0264 (3) | |
H8 | 0.4719 | 0.3663 | 0.5954 | 0.032* | |
C9 | 0.6720 (2) | 0.4370 (2) | 0.53162 (7) | 0.0267 (3) | |
H9 | 0.7691 | 0.3924 | 0.5573 | 0.032* | |
C10 | 0.7083 (2) | 0.5193 (2) | 0.47190 (7) | 0.0259 (3) | |
H10 | 0.8297 | 0.5343 | 0.4577 | 0.031* | |
C11 | 0.1222 (2) | 0.7095 (2) | 0.30450 (8) | 0.0329 (3) | |
H11A | 0.0183 | 0.6297 | 0.3103 | 0.049* | |
H11B | 0.1547 | 0.7148 | 0.2581 | 0.049* | |
H11C | 0.0908 | 0.8295 | 0.3199 | 0.049* | |
O31 | 0.66470 (15) | 0.53406 (15) | 0.32328 (6) | 0.0266 (3) | |
H31 | 0.689 (3) | 0.585 (3) | 0.2903 (11) | 0.036 (6)* | |
O71 | 0.17572 (16) | 0.46923 (16) | 0.53358 (6) | 0.0288 (3) | |
H71 | 0.164 (4) | 0.416 (3) | 0.5726 (14) | 0.055 (7)* | |
Cl1 | 0.23462 (5) | 0.24143 (5) | 0.300840 (16) | 0.02720 (12) | |
O1W | 0.13199 (19) | 0.32949 (16) | 0.65313 (6) | 0.0327 (3) | |
H1WA | 0.158 (4) | 0.215 (3) | 0.6527 (12) | 0.048 (6)* | |
H1WB | 0.014 (4) | 0.328 (4) | 0.6626 (13) | 0.059 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0220 (6) | 0.0246 (6) | 0.0208 (6) | 0.0007 (5) | −0.0004 (5) | 0.0000 (4) |
C2 | 0.0270 (7) | 0.0229 (6) | 0.0258 (6) | −0.0009 (6) | 0.0040 (5) | 0.0023 (6) |
C3 | 0.0227 (7) | 0.0214 (6) | 0.0235 (7) | −0.0017 (6) | 0.0035 (6) | −0.0011 (5) |
C4 | 0.0243 (7) | 0.0224 (6) | 0.0191 (6) | −0.0011 (5) | 0.0001 (5) | −0.0024 (5) |
C5 | 0.0230 (7) | 0.0209 (6) | 0.0201 (6) | −0.0006 (6) | 0.0009 (5) | −0.0017 (5) |
C6 | 0.0199 (6) | 0.0260 (6) | 0.0210 (6) | 0.0001 (5) | 0.0023 (5) | 0.0005 (5) |
C7 | 0.0258 (7) | 0.0224 (6) | 0.0207 (6) | −0.0007 (5) | 0.0019 (6) | −0.0023 (5) |
C8 | 0.0342 (8) | 0.0244 (7) | 0.0207 (6) | 0.0003 (6) | −0.0014 (6) | −0.0009 (5) |
C9 | 0.0280 (7) | 0.0281 (7) | 0.0238 (7) | 0.0017 (6) | −0.0066 (6) | −0.0016 (6) |
C10 | 0.0218 (7) | 0.0312 (7) | 0.0248 (7) | −0.0020 (6) | −0.0009 (6) | −0.0039 (6) |
C11 | 0.0265 (7) | 0.0426 (8) | 0.0295 (7) | 0.0063 (6) | −0.0046 (6) | 0.0075 (7) |
O31 | 0.0311 (6) | 0.0263 (5) | 0.0222 (5) | 0.0014 (5) | 0.0081 (5) | 0.0011 (4) |
O71 | 0.0274 (6) | 0.0329 (6) | 0.0262 (5) | −0.0015 (5) | 0.0054 (5) | 0.0039 (5) |
Cl1 | 0.02922 (18) | 0.02989 (18) | 0.02250 (17) | −0.00307 (15) | 0.00038 (13) | −0.00474 (13) |
O1W | 0.0373 (7) | 0.0282 (6) | 0.0325 (6) | −0.0009 (5) | 0.0079 (5) | 0.0043 (5) |
N1—C2 | 1.4957 (19) | C6—H6B | 0.9900 |
N1—C11 | 1.500 (2) | C7—O71 | 1.3611 (19) |
N1—C6 | 1.5017 (18) | C7—C8 | 1.393 (2) |
N1—H1 | 0.94 (2) | C8—C9 | 1.392 (2) |
C2—C3 | 1.519 (2) | C8—H8 | 0.9500 |
C2—H2A | 0.9900 | C9—C10 | 1.395 (2) |
C2—H2B | 0.9900 | C9—H9 | 0.9500 |
C3—O31 | 1.4369 (18) | C10—H10 | 0.9500 |
C3—C4 | 1.5218 (19) | C11—H11A | 0.9800 |
C3—H3 | 1.0000 | C11—H11B | 0.9800 |
C4—C10 | 1.396 (2) | C11—H11C | 0.9800 |
C4—C5 | 1.398 (2) | O31—H31 | 0.79 (2) |
C5—C7 | 1.407 (2) | O71—H71 | 0.90 (3) |
C5—C6 | 1.507 (2) | O1W—H1WA | 0.88 (3) |
C6—H6A | 0.9900 | O1W—H1WB | 0.89 (3) |
C2—N1—C11 | 112.12 (12) | C5—C6—H6A | 109.4 |
C2—N1—C6 | 110.38 (11) | N1—C6—H6B | 109.4 |
C11—N1—C6 | 110.57 (12) | C5—C6—H6B | 109.4 |
C2—N1—H1 | 113.3 (13) | H6A—C6—H6B | 108.0 |
C11—N1—H1 | 106.7 (13) | O71—C7—C8 | 123.60 (14) |
C6—N1—H1 | 103.4 (12) | O71—C7—C5 | 116.10 (14) |
N1—C2—C3 | 109.47 (11) | C8—C7—C5 | 120.29 (14) |
N1—C2—H2A | 109.8 | C9—C8—C7 | 119.47 (14) |
C3—C2—H2A | 109.8 | C9—C8—H8 | 120.3 |
N1—C2—H2B | 109.8 | C7—C8—H8 | 120.3 |
C3—C2—H2B | 109.8 | C8—C9—C10 | 120.83 (14) |
H2A—C2—H2B | 108.2 | C8—C9—H9 | 119.6 |
O31—C3—C2 | 110.32 (12) | C10—C9—H9 | 119.6 |
O31—C3—C4 | 107.67 (11) | C9—C10—C4 | 119.65 (14) |
C2—C3—C4 | 111.96 (12) | C9—C10—H10 | 120.2 |
O31—C3—H3 | 108.9 | C4—C10—H10 | 120.2 |
C2—C3—H3 | 108.9 | N1—C11—H11A | 109.5 |
C4—C3—H3 | 108.9 | N1—C11—H11B | 109.5 |
C10—C4—C5 | 120.15 (13) | H11A—C11—H11B | 109.5 |
C10—C4—C3 | 119.93 (13) | N1—C11—H11C | 109.5 |
C5—C4—C3 | 119.92 (13) | H11A—C11—H11C | 109.5 |
C4—C5—C7 | 119.48 (13) | H11B—C11—H11C | 109.5 |
C4—C5—C6 | 123.27 (12) | C3—O31—H31 | 105.8 (16) |
C7—C5—C6 | 117.24 (13) | C7—O71—H71 | 111.2 (18) |
N1—C6—C5 | 111.15 (12) | H1WA—O1W—H1WB | 102 (3) |
N1—C6—H6A | 109.4 | ||
C11—N1—C2—C3 | −167.99 (12) | C11—N1—C6—C5 | −173.04 (12) |
C6—N1—C2—C3 | 68.26 (15) | C4—C5—C6—N1 | 12.93 (18) |
N1—C2—C3—O31 | 70.79 (15) | C7—C5—C6—N1 | −165.99 (12) |
N1—C2—C3—C4 | −49.10 (16) | C4—C5—C7—O71 | 176.75 (13) |
O31—C3—C4—C10 | 72.13 (16) | C6—C5—C7—O71 | −4.29 (19) |
C2—C3—C4—C10 | −166.44 (13) | C4—C5—C7—C8 | −3.9 (2) |
O31—C3—C4—C5 | −107.27 (15) | C6—C5—C7—C8 | 175.06 (13) |
C2—C3—C4—C5 | 14.16 (18) | O71—C7—C8—C9 | −179.57 (15) |
C10—C4—C5—C7 | 3.7 (2) | C5—C7—C8—C9 | 1.1 (2) |
C3—C4—C5—C7 | −176.94 (12) | C7—C8—C9—C10 | 1.9 (2) |
C10—C4—C5—C6 | −175.23 (14) | C8—C9—C10—C4 | −2.1 (2) |
C3—C4—C5—C6 | 4.2 (2) | C5—C4—C10—C9 | −0.7 (2) |
C2—N1—C6—C5 | −48.40 (15) | C3—C4—C10—C9 | 179.92 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O31i | 0.88 (3) | 1.93 (3) | 2.7733 (17) | 161 (2) |
N1—H1···Cl1 | 0.94 (2) | 2.25 (2) | 3.1204 (13) | 153.6 (17) |
O31—H31···Cl1ii | 0.79 (2) | 2.28 (2) | 3.0682 (12) | 177 (2) |
O71—H71···O1W | 0.90 (3) | 1.79 (3) | 2.6803 (17) | 174 (2) |
O1W—H1WB···Cl1i | 0.89 (3) | 2.26 (3) | 3.1299 (14) | 165 (3) |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C10H14NO2+·Cl−·H2O |
Mr | 233.69 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 173 |
a, b, c (Å) | 7.3919 (7), 7.4823 (7), 20.4655 (17) |
V (Å3) | 1131.91 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.33 |
Crystal size (mm) | 0.49 × 0.48 × 0.45 |
Data collection | |
Diffractometer | Stoe IPDSII two-circle |
Absorption correction | Multi-scan (MULABS; Spek, 2003; Blessing, 1995) |
Tmin, Tmax | 0.857, 0.868 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6824, 2586, 2490 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.079, 1.07 |
No. of reflections | 2586 |
No. of parameters | 158 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.23, −0.18 |
Absolute structure | Flack (1983), 1057 Friedel pairs |
Absolute structure parameter | 0.02 (6) |
Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O31i | 0.88 (3) | 1.93 (3) | 2.7733 (17) | 161 (2) |
N1—H1···Cl1 | 0.94 (2) | 2.25 (2) | 3.1204 (13) | 153.6 (17) |
O31—H31···Cl1ii | 0.79 (2) | 2.28 (2) | 3.0682 (12) | 177 (2) |
O71—H71···O1W | 0.90 (3) | 1.79 (3) | 2.6803 (17) | 174 (2) |
O1W—H1WB···Cl1i | 0.89 (3) | 2.26 (3) | 3.1299 (14) | 165 (3) |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) −x+1, y+1/2, −z+1/2. |
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.