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ISSN: 2056-9890

Crystal structure of 2-methyl-1,2,3,4-tetra­hydro­iso­quinoline trihydrate

aTechnical University Dortmund, Inorganic Chemistry, Otto-Hahn-Strasse 6, D-44227, Dortmund, Germany
*Correspondence e-mail: carsten.strohmann@tu-dortmund.de

Edited by M. Zeller, Purdue University, USA (Received 9 December 2019; accepted 21 January 2020; online 6 February 2020)

The crystal structure of the title compound, C10H13N·3H2O, a heterocyclic amine, was determined in the presence of water. The compound co-crystallizes with three water mol­ecules in the asymmetric unit, which leads to the formation of hydrogen bonding in the crystal.

1. Chemical context

Tetra­hydro­iso­quinolines are heterocyclic secondary amines that can be found in animal and human brains (Rommelspacher & Susilo, 1985[Rommelspacher, H. & Susilo, R. (1985). Progress in Drug Research, edited by E. Jucker, pp. 415-459. Basel: Brikhäuser Basel.]). Many compounds of this class and their derivatives are bioactive and show promising pharmacological potential, for example as neuroprotectants or anti­tumor anti­biotics (Scott & Williams, 2002[Scott, J. D. & Williams, R. M. (2002). Chem. Rev. 102, 1669-1730.]; Antkiewicz-Michaluk et al., 2014[Antkiewicz-Michaluk, L., Wąsik, A. & Michaluk, J. (2014). Neurotox. Res. 25, 1-12.]). Studies show that some of these endogenous compounds function as Parkinsonism-inducing agents, while others can prevent Parkinsonism and are therefore promising candidates for treatment of Parkinson's disease (Kotake et al., 1995[Kotake, Y., Tasaki, Y., Makino, Y., Ohta, S. & Hirobe, M. (1995). J. Neurochem. 65, 2633-2638.]; Lorenc-Koci et al., 1999[Lorenc-Koci, E., ŚmiaŁowska, M., Antkiewicz-Michaluk, L., GoŁembiowska, K., Bajkowska, M. & Wolfarth, S. (1999). Neuroscience, 95, 1049-1059.], 2008[Lorenc-Koci, E., Antkiewicz-Michaluk, L., Kamińska, A., Lenda, T., Zięba, B., Wierońska, J., Śmiałowska, M., Schulze, G. & Rommelspacher, H. (2008). Neuroscience, 156, 973-986.]; McNaught et al., 1998[McNaught, K. S. P., Carrupt, P.-A., Altomare, C., Cellamare, S., Carotti, A., Testa, B., Jenner, P. & Marsden, C. D. (1998). Biochem. Pharmacol. 56, 921-933.]; Storch et al., 2002[Storch, A., Ott, S., Hwang, Y.-I., Ortmann, R., Hein, A., Frenzel, S., Matsubara, K., Ohta, S., Wolf, H.-U. & Schwarz, J. (2002). Biochem. Pharmacol. 63, 909-920.]). Their structures are therefore analysed to gain a better understanding of their function and possible chemical and pharmaceutical properties. In this case, we report the crystal structure of 2-methyl-1,2,3,4,-tetra­hydro­iso­quinoline, which co-crystallizes with water.

[Scheme 1]

2. Structural commentary

The heterocyclic amine, itself an oil at room temperature, crystallizes in the presence of water at 243 K, and crystals are stable up to ca 273 K when they melt. The asymmetric unit of the mol­ecular structure, in space group P21/c, is illustrated in Fig. 1[link]. In addition to the heterocyclic amine, the asymmetric unit contains three water mol­ecules, which make up 27 mass % of the crystal. For poorly crystallizing organic compounds containing hydrogen-bond acceptors with weak polar inter­actions (such as the title compound), crystallization in the presence of water and therefore the formation of hydrate compounds seems to be an alternative strategy for crystal formation and/or purification. This holds true especially when the formation of ions, e.g. hydro­chlorides, is not desired to avoid structural changes caused by derivatization of the compounds.

[Figure 1]
Figure 1
Asymmetric unit and mol­ecular structure in the crystal of the title compound with the unit-cell boundaries and atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

The amine exhibits typical bond lengths and angles in the expected ranges (Allen et al., 1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-S19.]). The compound contains two different ring systems. The aromatic ring (C4/C5/C7–C10) is planar as expected, while the non-aromatic ring (N1/C2-C6) has a half-boat conformation and can be described with the Cremer–Pople parameters with a total puckering amplitude of QT = 0.5067 (11) Å, an azimuthal angle (θ) of 133.22 (12)° and a zenithal angle (Φ) of 208.82 (18)°. The structure is comparable with those of other tetra­hydro­isochinoline derivatives such as 2-(2-chloro­acet­yl)-6,7-dimeth­oxy-1,2,3,4-tetra­hydro­iso­quinoline (Ling et al., 2006[Ling, Y., Xu, H., Zou, Z.-H. & Yao, C. (2006). Acta Cryst. E62, o2775-o2777.]) or 5-(6,7-dimeth­oxy-1,2,3,4-tetra­hydro­isoquinolin-2-yl)-4-phenyl-1,2,5-oxa­diazole N-oxide (Xu et al., 2006[Xu, H., Ling, Y., Zou, Z.-H., Huang, W.-L. & Yao, C. (2006). Acta Cryst. E62, o3130-o3132.]), that also show a half-boat conformation of the non-planar ring. The nitro­gen atom displays a tetra­hedral environment, which indicates an sp3 hybridization, as is to be expected for a tertiary amine. This is similar to the tetra­hydro­iso­quinoline published by Xu et al., but in comparison the mentioned structure from Ling et al. shows a trigonal planar sp2-hybridized nitro­gen atom. Some selected bond lengths and angles are listed in Table 1[link].

Table 1
Selected geometric parameters (Å, °)

N1—C1 1.4678 (14) N1—C6 1.4671 (13)
N1—C2 1.4708 (14) C4—C5 1.3977 (13)
       
C1—N1—C2 110.91 (9) N1—C2—C3 109.72 (9)
C6—N1—C1 109.43 (8) N1—C6—C5 112.77 (8)
C6—N1—C2 110.12 (8) C4—C3—C2 112.45 (9)

3. Supra­molecular features

As a result of the high amount of crystal water, an extensive supra­molecular hydrogen-bonding network is formed. Geometrical details of the hydrogen bonding are listed in Table 2[link].

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1D⋯N1 0.94 (2) 1.81 (2) 2.7394 (12) 170.7 (18)
O1—H1E⋯O2i 0.95 (2) 1.81 (2) 2.7635 (12) 176 (2)
O3—H3C⋯O2 0.86 (2) 1.96 (2) 2.8070 (13) 165.8 (19)
O3—H3D⋯O1ii 0.91 (2) 1.84 (2) 2.7461 (12) 175.1 (19)
O2—H2C⋯O1 0.92 (2) 1.84 (2) 2.7538 (12) 174.9 (19)
O2—H2D⋯O3iii 0.88 (2) 1.88 (2) 2.7512 (13) 173 (2)
C6—H6A⋯O3i 0.98 (2) 2.49 (2) 3.4531 (3) 168.8 (2)
Symmetry codes: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) -x+1, -y+2, -z+2; (iii) -x+1, -y+1, -z+2.

The crystal water forms a matrix in the bc plane, to which the amines are bound with the help of another set of hydrogen bonds. A section of the supra­molecular hydrogen bonding and crystal packing along the b-axis direction is shown in Fig. 2[link]. In this view the water forms a channel along the c axis, and the bridging of the organic mol­ecules by the nitro­gen atoms is clearly visible. The organic mol­ecules are stacked in parallel along the b axis with a distance of 5.9209 (6) Å. The iso­quinolines on the other side of the infinite water channel are invertedly aligned along the c axis. This also results in the formation of alternating hydro­philic and hydro­phobic phases of the hydrogen-bonded water framework and organic phases of the heterocyclic amines along the a axis.

[Figure 2]
Figure 2
View along the b axis through the crystal packing shows the hydrogen-bonding network, the parallel stacked organic mol­ecules and reveals the alternating hydro­phobic and hydro­philic packing phases.

An alternative view of the crystal packing along the c axis shows that the heterocyclic amines are alternately connected to the hydrogen-bonding system along the axis, which leads in the formation of syndiotactic polymer chains in this dimension (see Fig. 3[link]).

[Figure 3]
Figure 3
View along the c axis through the crystal packing showing the other side of the hydrogen-bonding network and the different arrangement of the organic mol­ecules.

An analysis of the hydrogen-bonding network formed by the water mol­ecules is illustrated in Fig. 4[link]. Here the view along the a axis shows the formed water plane along the b and c axes with different ring systems (only counting the oxygen atoms) and the graph-set motifs of the hydrogen-bonding network. The infinite hydrogen-bonded network is formed along the c axis by chains of connected five-membered [R55 (10)] rings (connected via hydrogen bond b) followed by chains of alternating four- and six-membered [R44 (8)] and [R64 (12)] rings (connected via hydrogen bond c) that are orientated along the b axis.

[Figure 4]
Figure 4
View along the a axis through the crystal packing shows the hydrogen-bonding network. For a better view, only one amine mol­ecule is shown, to highlight the supra­molecular water network in the bc plane. The various hydrogen bonds are labelled as examples for a four-, five- and sex-membered ring (red bf), as well as an amine hydrogen bond (green a).

For the third oxygen atom (O3), the ideal tetra­hedral environment (Bernal & Fowler, 1933[Bernal, J. D. & Fowler, R. H. (1933). J. Chem. Phys. 1, 515-548.]) is achieved by formation of a weak hydrogen bond to the H6A hydrogen atom of the alpha carbon atom (C6), which is indicated by the short C6⋯O3 distance [3.4531 (3) Å]. This can be highlighted by an Hirshfeld surface analysis, shown in Fig. 5[link]. The short distance alone is not a clear evidence for a weak hydrogen bond, however the linear angle C6—H6A⋯O3 of 168.8 (2)° (without cone-correction; Kroon & Kanters, 1974[Kroon, J. & Kanters, J. A. (1974). Nature, 248, 667-669.]) strongly supports this assumption. For an overview of the definition and characteristics of weak hydrogen bonding, see, for example: Desiraju & Steiner (1999[Desiraju, G. R. & Steiner, T. (1999). In The Weak Hydrogen Bond in Structural Chemistry and Biology. Oxford University Press.]).

[Figure 5]
Figure 5
Hirshfeld-surface analysis (CrystalExplorer17; Turner et al., 2017[Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. University of Western Australia.]) of the compound displays close contacts in the crystal. The weak hydrogen bond between oxygen atom O3 and the H6A hydrogen atom is labelled. Symmetry codes: (i) 1 – x, [{1\over 2}] + y, 3/2 – z; (ii) 1 – x, 1 – y, 2 – z.

4. Database survey

A survey of the Cambridge Crystallographic Database (CSD, Version 5.40, September 2019; Groom et al., 2016[Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171-179.]) shows about 1000 results for structures where the investigated amine is a substructure of a more complex structure. The before-mentioned compounds C13H16ClNO3 (Ling et al., 2006[Ling, Y., Xu, H., Zou, Z.-H. & Yao, C. (2006). Acta Cryst. E62, o2775-o2777.]) and C20H21N3O4 (Xu et al., 2006[Xu, H., Ling, Y., Zou, Z.-H., Huang, W.-L. & Yao, C. (2006). Acta Cryst. E62, o3130-o3132.]) are two examples of this. Moreover, some others are C19H17NO5 (Aree et al., 2003[Aree, T., Singhana, B., Pakawatchai, C., Chavasiri, W. & Kokpol, U. (2003). Acta Cryst. E59, o919-o921.]), C24H23NO2 (Philippe et al., 2000[Philippe, N., Levacher, V., Dupas, G., Quéguiner, G. & Bourguignon, J. (2000). Org. Lett. 2, 2185-2187.]), C15H17NO3 (Li et al., 2011[Li, W.-D. Z., Duo, W.-G. & Zhuang, C.-H. (2011). Org. Lett. 13, 3538-3541.]) and C22H23NO6 (Roques et al., 1978[Roques, R., Declercq, J. P. & Germain, G. (1978). Acta Cryst. B34, 2017-2020.]). Another example for a reported crystal structure is C24H25NO3·2CH3OH, which is used as a PET radiotracer and has been tested in clinical evaluation for early diagnosis of Alzheimer's disease (Altomare et al., 2014[Altomare, A., Capparelli, E., Carrieri, A., Colabufo, N. A., Moliterni, A., Rizzi, R. & Siliqi, D. (2014). Acta Cryst. E70, o1149-o1150.]). All derivates found during the survey have in common that they have more complex structures and are often O-functionalized compared to the title compound. Some small reported analogues of this compound are metallated derivatives with lithium and potassium, which were published in a study about stabilization of different amine anions by our group (Unkelbach et al., 2012[Unkelbach, C., Rosenbaum, H. S. & Strohmann, C. (2012). Chem. Commun. 48, 10612-10614.]).

5. Synthesis and crystallization

1,2,3,4-Tetra­hydro­iso­quinoline (10 mL, 79.66 mmol) was dissolved in 30 mL of formic acid (99%). After adding formaldehyde (30 mL, 37% in water) the solution was stirred under reflux for 6 h and stirred at room temperature for an additional 12 h. Subsequently KOH was added to adjust to pH 13. In the next step, the two-phase system was extracted with diethyl ether (3 x 50 mL). The combined organic phases were dried with MgSO4. After removing the solvent the raw product was distilled (333 K, 0.25 mbar) and the pure amine could be obtained as a colourless oil (94% yield).

The title compound crystallizes in the presence of water, by adding some drops of water to a solution of the amine in Et2O, mixing the two phases and then separating again to obtain a moist organic phase. Storage of the organic phase at 243 K results in crystallization of the title compound in colourless needles, which are stable up to 273 K before they start melting. The crystals were therefore selected for measurement with help of a X-Temp 2 low-temperature stage (Heine & Stalke, 1992[Heine, A. & Stalke, D. (1992). Angew. Chem. Int. Ed. Engl. 31, 854-855.]; Stalke, 1998[Stalke, D. (1998). Chem. Soc. Rev. 27, 171-178.]).

The pure amine is known from the literature and the measured analytical NMR and MS data correspond to the reported data (Locher & Peerzada, 1999[Locher, C. & Peerzada, N. (1999). J. Chem. Soc. Perkin Trans. 1, pp. 179-184.]).

1H NMR (CDCl3, 400 MHz): δ (ppm) 2.48 (3H, s, NCH3), 2.72 (2H, t, NCH2CH2), 2.95 (2H, t, NCH2CH2), 3.61 (2H, s, NCH2Car, 7.02–7.04 (1H, m, CHar), 7.11–7.15 (3H, m, CHar).

13C NMR (CDCl3, 100 MHz): δ (ppm) 29.1 (1C, CarCH2CH2), 46.0 (1C, NCH3), 52.8 (NCH2CH2), 57.9 (CarCH2N), 125.6 (1C, Car), 126.4 (1C, Car), 128.6 (1C, Car), 133.7 (1C, Car), 134.5 (1C, Car).

GC/MS (EI) m/z (intensity %): 146 (100) [M–H]+ 131 (9) [M–CH3–H]+, 104 (51).

Elemental analysis calculated (%) for C10H13Ni: C 81.6, H 8.9, N 9.5; found: C 81.2, H 9.0, N 9.6.

Because of the low stability of the crystals of the trihydrate, no further analysis of the trihydrate was carried out, except for NMR spectroscopy of the crystals, which reveals a broadened water signal in the 1H NMR spectrum, which overlaps with other signals in d-aceto­nitrile.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. The C-bound hydrogen atoms of the amine, except the protons H6A and H6B, were included in calculated positions with C—H = 0.95 Å, Uiso(H) = 1.2Ueq(C) for aromatic hydrogen atoms, C—H = 0.99 Å, Uiso(H) = 1.2Ueq(C) for CH2 hydrogen atoms and with C—H = 0.98 Å, Uiso(H) = 1.5 Ueq(C) for methyl hydrogen atoms. All other protons were located in the difference-Fourier maps and refined freely.

Table 3
Experimental details

Crystal data
Chemical formula C10H13N·3H2O
Mr 201.26
Crystal system, space group Monoclinic, P21/c
Temperature (K) 100
a, b, c (Å) 16.1791 (19), 5.9209 (6), 12.5007 (14)
β (°) 106.093 (5)
V3) 1150.6 (2)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.09
Crystal size (mm) 0.51 × 0.09 × 0.05
 
Data collection
Diffractometer Bruker D8 Venture
Absorption correction Multi-scan (SADABS; Bruker, 2016[Bruker (2016). SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.655, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections 13488, 3350, 2708
Rint 0.042
(sin θ/λ)max−1) 0.703
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.109, 1.03
No. of reflections 3350
No. of parameters 160
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.35, −0.20
Computer programs: APEX3 (Bruker, 2018[Bruker (2018). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]), SAINT (Bruker, 2016[Bruker (2016). SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXT (Sheldrick, 2015a[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]), SHELXL (Sheldrick, 2015b[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]), OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]), PLATON (Spek, 2020[Spek, A. L. (2020). Acta Cryst. E76, 1-11.]), publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]).

Supporting information


Computing details top

Data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009), PLATON (Spek, 2020), publCIF (Westrip, 2010) and Mercury (Macrae et al., 2008).

2-Methyl-1,2,3,4-tetrahydroisoquinoline trihydrate top
Crystal data top
C10H13N·3H2OF(000) = 440
Mr = 201.26Dx = 1.162 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 16.1791 (19) ÅCell parameters from 5564 reflections
b = 5.9209 (6) Åθ = 2.6–30.5°
c = 12.5007 (14) ŵ = 0.09 mm1
β = 106.093 (5)°T = 100 K
V = 1150.6 (2) Å3Needle, colourless
Z = 40.51 × 0.09 × 0.05 mm
Data collection top
Bruker D8 Venture
diffractometer
3350 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs2708 reflections with I > 2σ(I)
HELIOS mirror optics monochromatorRint = 0.042
Detector resolution: 10.4167 pixels mm-1θmax = 30.0°, θmin = 2.6°
ω and φ scansh = 2222
Absorption correction: multi-scan
(SADABS; Bruker, 2016)
k = 88
Tmin = 0.655, Tmax = 0.746l = 1717
13488 measured reflections
Refinement top
Refinement on F2Primary atom site location: dual
Least-squares matrix: fullSecondary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: mixed
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.045P)2 + 0.3326P]
where P = (Fo2 + 2Fc2)/3
3350 reflections(Δ/σ)max = 0.001
160 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = 0.20 e Å3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.59406 (5)1.05257 (14)0.81663 (7)0.02252 (18)
H1D0.6378 (12)0.971 (3)0.7983 (16)0.056 (5)*
H1E0.5579 (14)1.109 (4)0.7482 (19)0.074 (6)*
O30.39039 (6)0.63708 (15)1.01569 (7)0.02562 (19)
H3C0.4235 (13)0.685 (3)0.9772 (17)0.062 (6)*
H3D0.3929 (13)0.744 (4)1.0688 (17)0.062 (6)*
O20.50431 (6)0.71399 (15)0.88618 (7)0.02490 (19)
H2C0.5355 (14)0.830 (4)0.8673 (17)0.066 (6)*
H2D0.5419 (14)0.609 (4)0.9175 (17)0.063 (6)*
N10.71223 (6)0.77354 (16)0.76435 (7)0.01927 (19)
C10.65506 (8)0.5945 (2)0.70453 (10)0.0274 (2)
H1A0.6169340.6561090.6356470.041*
H1B0.6204790.5361100.7515450.041*
H1C0.6895970.4719120.6864700.041*
C20.77022 (7)0.68697 (19)0.86859 (9)0.0219 (2)
H2A0.8112820.5781620.8515500.026*
H2B0.7364180.6071420.9119100.026*
C30.81920 (7)0.8817 (2)0.93665 (8)0.0219 (2)
H3A0.7793770.9705480.9676250.026*
H3B0.8649660.8203960.9998650.026*
C40.85940 (6)1.03588 (18)0.86857 (8)0.0176 (2)
C50.82967 (6)1.03240 (18)0.75240 (8)0.0173 (2)
C60.76234 (7)0.86499 (19)0.69280 (8)0.0201 (2)
H6A0.7237 (9)0.935 (2)0.6266 (12)0.025 (3)*
H6B0.7924 (9)0.735 (3)0.6644 (12)0.031 (4)*
C70.92500 (7)1.18598 (19)0.91984 (8)0.0198 (2)
H70.9458261.1881630.9987460.024*
C80.96030 (7)1.33188 (19)0.85767 (9)0.0213 (2)
H81.0050491.4325940.8938170.026*
C90.92978 (7)1.33005 (19)0.74177 (9)0.0220 (2)
H90.9533931.4298760.6984930.026*
C100.86485 (7)1.18171 (19)0.69038 (8)0.0204 (2)
H100.8438081.1813630.6114780.024*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0237 (4)0.0211 (4)0.0236 (4)0.0030 (3)0.0079 (3)0.0008 (3)
O30.0303 (4)0.0251 (4)0.0223 (4)0.0020 (3)0.0086 (3)0.0023 (3)
O20.0270 (4)0.0234 (4)0.0255 (4)0.0006 (3)0.0091 (3)0.0030 (3)
N10.0197 (4)0.0194 (4)0.0192 (4)0.0010 (3)0.0063 (3)0.0001 (3)
C10.0287 (6)0.0240 (6)0.0301 (6)0.0063 (5)0.0092 (5)0.0064 (4)
C20.0236 (5)0.0219 (5)0.0219 (5)0.0026 (4)0.0091 (4)0.0053 (4)
C30.0212 (5)0.0287 (6)0.0163 (4)0.0002 (4)0.0063 (4)0.0056 (4)
C40.0176 (5)0.0208 (5)0.0158 (4)0.0038 (4)0.0068 (4)0.0026 (4)
C50.0172 (5)0.0199 (5)0.0160 (4)0.0038 (4)0.0066 (4)0.0015 (4)
C60.0216 (5)0.0237 (5)0.0157 (4)0.0008 (4)0.0065 (4)0.0004 (4)
C70.0197 (5)0.0243 (5)0.0160 (4)0.0034 (4)0.0059 (4)0.0001 (4)
C80.0199 (5)0.0221 (5)0.0230 (5)0.0010 (4)0.0077 (4)0.0024 (4)
C90.0247 (5)0.0230 (5)0.0217 (5)0.0008 (4)0.0122 (4)0.0031 (4)
C100.0231 (5)0.0241 (5)0.0157 (4)0.0023 (4)0.0084 (4)0.0021 (4)
Geometric parameters (Å, º) top
O1—H1D0.94 (2)C3—H3B0.9900
O1—H1E0.95 (2)C3—C41.5124 (14)
O3—H3C0.86 (2)C4—C51.3977 (13)
O3—H3D0.91 (2)C4—C71.3964 (15)
O2—H2C0.92 (2)C5—C61.5081 (15)
O2—H2D0.88 (2)C5—C101.3968 (14)
N1—C11.4678 (14)C6—H6A0.980 (14)
N1—C21.4708 (14)C6—H6B1.022 (15)
N1—C61.4671 (13)C7—H70.9500
C1—H1A0.9800C7—C81.3865 (15)
C1—H1B0.9800C8—H80.9500
C1—H1C0.9800C8—C91.3952 (15)
C2—H2A0.9900C9—H90.9500
C2—H2B0.9900C9—C101.3833 (16)
C2—C31.5190 (16)C10—H100.9500
C3—H3A0.9900
H1D—O1—H1E106.2 (17)C4—C3—H3B109.1
H3C—O3—H3D105.7 (18)C5—C4—C3119.87 (10)
H2C—O2—H2D106.2 (18)C7—C4—C3121.11 (9)
C1—N1—C2110.91 (9)C7—C4—C5119.01 (9)
C6—N1—C1109.43 (8)C4—C5—C6121.09 (9)
C6—N1—C2110.12 (8)C10—C5—C4119.45 (10)
N1—C1—H1A109.5C10—C5—C6119.44 (9)
N1—C1—H1B109.5N1—C6—H6A109.8 (8)
N1—C1—H1C109.5N1—C6—H6B109.3 (8)
H1A—C1—H1B109.5C5—C6—H6A110.2 (8)
H1A—C1—H1C109.5C5—C6—H6B108.5 (8)
H1B—C1—H1C109.5H6A—C6—H6B106.1 (11)
N1—C2—H2A109.7C4—C7—H7119.4
N1—C2—H2B109.7C8—C7—C4121.21 (9)
N1—C2—C3109.72 (9)C8—C7—H7119.4
H2A—C2—H2B108.2C7—C8—H8120.2
C3—C2—H2A109.7C7—C8—C9119.67 (10)
C3—C2—H2B109.7C9—C8—H8120.2
C2—C3—H3A109.1C8—C9—H9120.3
C2—C3—H3B109.1C10—C9—C8119.46 (10)
H3A—C3—H3B107.8C10—C9—H9120.3
N1—C6—C5112.77 (8)C5—C10—H10119.4
C4—C3—C2112.45 (9)C9—C10—C5121.19 (10)
C4—C3—H3A109.1C9—C10—H10119.4
N1—C2—C3—C449.12 (12)C4—C5—C10—C91.27 (16)
C1—N1—C2—C3171.72 (9)C4—C7—C8—C90.23 (16)
C1—N1—C6—C5173.75 (9)C5—C4—C7—C80.56 (16)
C2—N1—C6—C551.59 (12)C6—N1—C2—C367.00 (11)
C2—C3—C4—C518.69 (14)C6—C5—C10—C9176.74 (10)
C2—C3—C4—C7162.56 (10)C7—C4—C5—C6176.68 (9)
C3—C4—C5—C64.55 (15)C7—C4—C5—C101.29 (15)
C3—C4—C5—C10177.48 (10)C7—C8—C9—C100.28 (16)
C3—C4—C7—C8178.19 (10)C8—C9—C10—C50.47 (16)
C4—C5—C6—N120.70 (14)C10—C5—C6—N1161.33 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1D···N10.94 (2)1.81 (2)2.7394 (12)170.7 (18)
O1—H1E···O2i0.95 (2)1.81 (2)2.7635 (12)176 (2)
O3—H3C···O20.86 (2)1.96 (2)2.8070 (13)165.8 (19)
O3—H3D···O1ii0.91 (2)1.84 (2)2.7461 (12)175.1 (19)
O2—H2C···O10.92 (2)1.84 (2)2.7538 (12)174.9 (19)
O2—H2D···O3iii0.88 (2)1.88 (2)2.7512 (13)173 (2)
C6—H6A···O3i0.98 (2)2.49 (2)3.4531 (3)168.8 (2)
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x+1, y+2, z+2; (iii) x+1, y+1, z+2.
Selected geometric parameter (Å,°) top
N1–C11.4678 (14)N1–C61.4671 (13)
N1–C21.4708 (14)C4–C51.3977 (13)
C1–N1–C2110.91 (9)N1–C2–C3109.72 (9)
C1–N1–C6109.43 (8)N1–C6–C5112.77 (8)
C6–N1–C2110.12 (8)C4–C3–C2112.45 (9)

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