research communications
of levomepromazine maleate
aInstitute of Organic Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, H-1519 Budapest, POB 206, Hungary
*Correspondence e-mail: gal.tamas@ttk.mta.hu
The 19H25N2OS+·C4H3O4− [systematic name: (S)-3-(2-methoxyphenothiazin-10-yl)-N,N,2-trimethylpropanaminium hydrogen maleate], comprises two (S)-levomepromazine cations and two hydrogen maleate anions. The conformations of the two cations are similar. The major difference relates to the orientation of the methoxy substituent at the phenothiazine ring system. The crystal components form a three-dimensional supramolecular network via N—H⋯O, C—H⋯O and C—H⋯π interactions. A comparison of the conformations of the levomepromazine cations with those of the neutral molecule and similar protonated molecules reveals significant conformational flexibility of the phenothiazine ring system and the substituent at the phenothiazine N atom.
of the title salt, CKeywords: crystal structure; phenothiazine; maleate; hydrogen bonding; C—H⋯π interactions.
CCDC reference: 1470232
1. Chemical context
Levomepromazine maleate is a type of tranquilizer that is widely used as an important active pharmaceutical ingredient (API). As a typical N-substituted phenothiazine antipsychotic, this API is able to block a variety of receptors. For example, levomepromazine is used for treating schizophrenia (Froimowitz & Cody, 1993). The levomepromazine molecule is chiral and the (R)-(−) enantiomer is the medically active form. It is worth noting that the neutral (R)-levomepromazine molecule corresponds to the (S)-levomepromazine cation formed by protonation of its tertiary amino group, according to the Cahn–Ingold-Prelog (CIP) convention. The of neutral (R)-levomepromazine has been reported previously, including the determination of its (Sato et al.). As (R)-levomepromazine is generally sold in the form of its maleate salt, we report here the of this compound and compare the conformation of neutral levomepromazine with those of its cationic forms.
2. Structural commentary
The ). The nitrogen atoms N18 and N48 are protonated, thus the cations contain a tertiary amine group. The main difference in the cationic structures results from the different orientation of the methoxy substituent of the phenothiazine ring system, as illustrated in Fig. 2a where superposition of the two cations is presented. The root-mean-square deviation measuring the average distance between the atoms of the superimposed molecules is 0.509 Å and the maximum distance between the methoxy carbon atoms is 2.980 (4) Å. The phenothiazine groups are similarly bent along the N—S line with dihedral angles between the benzene rings of 42.51 (17) and 43.71 (18)°; these values are close to the analogous dihedral angles in the neutral levomepromazine molecule [41.24° at room temperature (MPZPAM; Sato et al., 1980) and 43.09° at 121 K (Dahl et al., 1982)].
of the title compound comprises two levomepromazine cations and two hydrogen maleate anions (Fig. 1The conformation of the investigated levomepromazine hydrogen maleate salt was compared with that of neutral levomepromazin (MPZPAM) and with the closely related compound 3-(2-methoxy-10-phenothiazinyl)-N,N-dimethyl-propanaminium hydrogen maleate, in which the propyl side chain is non-methylated (MAPTML10; Marsau & Gauthier, 1973) (see Fig. 2b). Molecules MPZPAM and MAPTML10 were inverted to obtain the same conformation for the phenothiazine rings (which resulted in the opposite enantiomer for MPZPAM). It can be seen that the main difference is in the torsion angle around the N10—C15 bond and the conformation of the side chain. For MPZPAM, the phenothiazine ring could be fully superimposed with the phenothiazine ring of the title compound, but the propyl side chains differ in the configuration and orientation of their aminomethyl groups. In the non-methylated derivative MAPTML10, the heterocyclic ring system is significantly closer to being flat (the dihedral angle between the benzene rings is 21.74°), while the aliphatic chain bends to the opposite site of the phenothiazine ring in comparison with the title compound.
The planar structure of the hydrogen maleate anions is stabilized by very strong intramolecular O—H⋯O hydrogen bonds between the carboxylic and carboxylate groups, as is often observed for these anions (Table 1, Fig. 3).
3. Supramolecular features
The ). The maleate anions form ionic pairs with the protonated amino groups of the levomepromazine cations by strong N—H⋯O interactions (Fig. 3). The methoxy groups of the levomepromazine cations differ in their intermolecular interactions. In one, the methoxy methyl group is involved in a C—H⋯π interaction to the aromatic ring of a neighbouring levomepromazine cation [C23—H23C⋯Cg(C31–C36), Table 1]. The same methyl group forms an additional hydrogen bond to a methoxy O atom of the other symmetry-independent levomepromazine cation (C23—H23A⋯O52, Fig. 4). There are numerous C—H⋯O interactions between the hydrogen maleate anions and the levomepromazine C—H groups, assisting the assembly of the crystal components in the bc plane (Table 1, Fig. 4).
of the title compound features strong N—H⋯O hydrogen bonds and several weak C—H⋯O interactions (Table 14. Synthesis and crystallization
The title compound was obtained from EGIS Pharmaceuticals Private Limited Company and used without further purification. The compound was enantiomerically pure, its melting point is 457–459 K. Colorless single crystals were obtained by slow evaporation of the solvent from an ethyl acetate solution over one week.
5. Refinement
Crystal data, data collection and details of the structure . The 13 missing reflections were found to be obstructed by the beamstop. All H atoms were located in difference electron-density maps. Hydrogen atoms were included in the structure-factor calculations but they were not refined; their positions were calculated with C—H = 0.95–1.00 Å and they were allowed to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C) for aromatic, methylene and methine and Uiso(H) = 1.5Ueq(C) for methyl protons. The around the C16 and C46 atoms in the title compound (Fig. 1) were determined to be S from effects.
are summarized in Table 2
|
Supporting information
CCDC reference: 1470232
10.1107/S2056989016004916/gk2652sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016004916/gk2652Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989016004916/gk2652Isup3.cml
Levomepromazine maleate is a type of tranquilizer that is widely used as an important active pharmaceutical ingredient (API). As a typical N-substituted phenothiazine antipsychotic, this API is able to block a variety of receptors. For example, levomepromazine is used for treating schizophrenia (Froimowitz & Cody, 1993). The levomepromazine molecule is chiral and the (R)-(-) enantiomer is the medically active form. It is worth noting that the neutral (R)-levomepromazine molecule corresponds to the (S)-levomepromazine cation formed by protonation of its tertiary amino group, according to the Cahn–Ingold-Prelog (CIP) convention. The
of neutral (R)- levomepromazine has been reported previously, including the determination of its (Sato et al.). As (R)- levomepromazine is generally sold in the form of its maleate salt, we report here the of this compound and compare the conformation of neutral levomepromazine with those of its cationic forms.The
of the title compound comprises two levomepromazine cations and two hydrogen maleate anions (Fig. 1). The nitrogen atoms N18 and N48 are protonated, thus the cations contain a tertiary amine group. The main difference in the cationic structures results from the different orientation of the methoxy substituent of the phenothiazine ring system, as illustrated in Fig. 2a where superposition of the two cations is presented. The root-mean-square deviation measuring the average distance between the atoms of the superimposed molecules is 0.509 Å and the maximum distance between the methoxy carbon atoms is 2.980 (4) Å. The phenothiazine groups are similarly bent along the N—S line with dihedral angles between the benzene rings of 42.51 (17) and 43.71 (18)°; these values are close to the analogous dihedral angles in the neutral levomepromazine molecule [41.24° at room temperature (MPZPAM; Sato et al., 1980) and 43.09° at 121 K (Dahl et al., 1982)].The conformation of the investigated levomepromazine hydrogen maleate salt was compared with that of neutral levomepromazin (MPZPAM) and with the closely related 3-(2-methoxy-10-phenothiazinyl)-N,N-dimethyl-propanaminium hydrogen maleate, for which the propyl side chain is non-methylated (MAPTML10; Marsau & Gauthier, 1973) (see Fig. 2b). Molecules MPZPAM and MAPTML10 were inverted to obtain the same conformation for the phenothiazine rings (which resulted in the opposite enantiomer for MPZPAM). It can be seen that the main difference is in the torsion angle around the N10—C15 bond and the conformation of the side chain. For MPZPAM, the phenothiazine ring could be fully superimposed with the phenothiazine ring of the title compound, but the propyl side chains differ in the configuration and orientation of their aminomethyl groups. In the non-methylated derivative MAPTML10, the heterocyclic ring system is significantly closer to being flat (the dihedral angle between the benzene rings is 21.74°), while the aliphatic chain bends to the opposite site of the phenothiazine ring in comparison with the title compound.
The planar structure of the hydrogen maleate anions is stabilized by very strong intramolecular O—H···O hydrogen bonds between the carboxylic and carboxylate groups, as is often observed for these anions (Table 1, Fig. 3).
The π interaction to the aromatic ring of the neighbouring levomepromazine cation [C23—H23C···Cg(C31–C36), Table 1]. The same methyl group forms an additional hydrogen bond to a methoxy O atom of the other symmetry-independent levomepromazine cation (C23—H23A···O52, Fig. 4). There are numerous C—H···O interactions between the hydrogen maleate anions and the levomepromazine C—H groups, assisting the assembly of the crystal components in the bc plane (Table 1, Fig. 4).
of the title compound is stabilized by strong N—H···O hydrogen bonds and several weak C—H···O interactions (Table 1). The maleate anions form ionic pairs with the protonated amino groups of the levomepromazine cations by strong N—H···O interactions (Fig. 3). The methoxy groups of the levomepromazine cations differ in their intermolecular interactions. In one, the methoxy methyl group is involved in a C—H···The title compound was obtained from EGIS Pharmaceuticals Private Limited Company and used without further purification. The compound was enantiomerically pure, its melting point is 457–459 K. Colorless single crystals were obtained by slow evaporation of the solvent from an ethyl acetate solution over one week.
Crystal data, data collection and details of the structure
are summarized in Table 2. The 13 missing reflections were found to be shaded by the beamstop. All H atoms were located in difference electron-density maps. Hydrogen atoms were included in the structure-factor calculations but they were not refined; their positions were calculated with C—H = 0.95–1.00 Å and they were allowed to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C) for aromatic, methylene and methine and Uiso(H) = 1.5Ueq(C) for methyl protons. The around the C16 and C46 atoms in the title compound (Fig. 1) were determined to be S from effects.Levomepromazine maleate is a type of tranquilizer that is widely used as an important active pharmaceutical ingredient (API). As a typical N-substituted phenothiazine antipsychotic, this API is able to block a variety of receptors. For example, levomepromazine is used for treating schizophrenia (Froimowitz & Cody, 1993). The levomepromazine molecule is chiral and the (R)-(-) enantiomer is the medically active form. It is worth noting that the neutral (R)-levomepromazine molecule corresponds to the (S)-levomepromazine cation formed by protonation of its tertiary amino group, according to the Cahn–Ingold-Prelog (CIP) convention. The
of neutral (R)- levomepromazine has been reported previously, including the determination of its (Sato et al.). As (R)- levomepromazine is generally sold in the form of its maleate salt, we report here the of this compound and compare the conformation of neutral levomepromazine with those of its cationic forms.The
of the title compound comprises two levomepromazine cations and two hydrogen maleate anions (Fig. 1). The nitrogen atoms N18 and N48 are protonated, thus the cations contain a tertiary amine group. The main difference in the cationic structures results from the different orientation of the methoxy substituent of the phenothiazine ring system, as illustrated in Fig. 2a where superposition of the two cations is presented. The root-mean-square deviation measuring the average distance between the atoms of the superimposed molecules is 0.509 Å and the maximum distance between the methoxy carbon atoms is 2.980 (4) Å. The phenothiazine groups are similarly bent along the N—S line with dihedral angles between the benzene rings of 42.51 (17) and 43.71 (18)°; these values are close to the analogous dihedral angles in the neutral levomepromazine molecule [41.24° at room temperature (MPZPAM; Sato et al., 1980) and 43.09° at 121 K (Dahl et al., 1982)].The conformation of the investigated levomepromazine hydrogen maleate salt was compared with that of neutral levomepromazin (MPZPAM) and with the closely related 3-(2-methoxy-10-phenothiazinyl)-N,N-dimethyl-propanaminium hydrogen maleate, for which the propyl side chain is non-methylated (MAPTML10; Marsau & Gauthier, 1973) (see Fig. 2b). Molecules MPZPAM and MAPTML10 were inverted to obtain the same conformation for the phenothiazine rings (which resulted in the opposite enantiomer for MPZPAM). It can be seen that the main difference is in the torsion angle around the N10—C15 bond and the conformation of the side chain. For MPZPAM, the phenothiazine ring could be fully superimposed with the phenothiazine ring of the title compound, but the propyl side chains differ in the configuration and orientation of their aminomethyl groups. In the non-methylated derivative MAPTML10, the heterocyclic ring system is significantly closer to being flat (the dihedral angle between the benzene rings is 21.74°), while the aliphatic chain bends to the opposite site of the phenothiazine ring in comparison with the title compound.
The planar structure of the hydrogen maleate anions is stabilized by very strong intramolecular O—H···O hydrogen bonds between the carboxylic and carboxylate groups, as is often observed for these anions (Table 1, Fig. 3).
The π interaction to the aromatic ring of the neighbouring levomepromazine cation [C23—H23C···Cg(C31–C36), Table 1]. The same methyl group forms an additional hydrogen bond to a methoxy O atom of the other symmetry-independent levomepromazine cation (C23—H23A···O52, Fig. 4). There are numerous C—H···O interactions between the hydrogen maleate anions and the levomepromazine C—H groups, assisting the assembly of the crystal components in the bc plane (Table 1, Fig. 4).
of the title compound is stabilized by strong N—H···O hydrogen bonds and several weak C—H···O interactions (Table 1). The maleate anions form ionic pairs with the protonated amino groups of the levomepromazine cations by strong N—H···O interactions (Fig. 3). The methoxy groups of the levomepromazine cations differ in their intermolecular interactions. In one, the methoxy methyl group is involved in a C—H···The title compound was obtained from EGIS Pharmaceuticals Private Limited Company and used without further purification. The compound was enantiomerically pure, its melting point is 457–459 K. Colorless single crystals were obtained by slow evaporation of the solvent from an ethyl acetate solution over one week.
detailsCrystal data, data collection and details of the structure
are summarized in Table 2. The 13 missing reflections were found to be shaded by the beamstop. All H atoms were located in difference electron-density maps. Hydrogen atoms were included in the structure-factor calculations but they were not refined; their positions were calculated with C—H = 0.95–1.00 Å and they were allowed to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C) for aromatic, methylene and methine and Uiso(H) = 1.5Ueq(C) for methyl protons. The around the C16 and C46 atoms in the title compound (Fig. 1) were determined to be S from effects.Data collection: CrystalClear (Rigaku/MSC, 2007); cell
CrystalClear (Rigaku/MSC, 2007); data reduction: CrystalClear (Rigaku/MSC, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: Mercury (Macrae et al., 2006) and PLATON (Spek, 2009).Fig. 1. The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The asymmetric unit contains two organic salt molecules. H atoms have been omitted for clarity. | |
Fig. 2. Conformational comparison of (a) the two levomepromazine molecules in the asymmetric unit of the title structure, and (b) one of the levomepromazines from the title structure (gray) compared with neutral dimorphic levomepromazine (green, MPZPAM) as well as the non-methylated derivative (purple, MAPTML10). | |
Fig. 3. The view of the columnar structure arrangement extending along the a axis showing the C—H···O and C—H···π interactions as turquoise lines. | |
Fig. 4. Crystal packing along the bc plane showing the N—H···O and C—H···O interactions in dashed lines. |
C19H25N2OS+·C4H3O4− | Dx = 1.299 Mg m−3 |
Mr = 444.53 | Melting point = 457–459 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.6395 (5) Å | Cell parameters from 74983 reflections |
b = 19.0487 (6) Å | θ = 3.2–27.5° |
c = 20.4977 (7) Å | µ = 0.18 mm−1 |
V = 4544.7 (3) Å3 | T = 103 K |
Z = 8 | Prism, colourless |
F(000) = 1888 | 0.5 × 0.3 × 0.2 mm |
R-AXIS RAPID diffractometer | 10363 independent reflections |
Radiation source: NORMAL-focus sealed tube | 8459 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.085 |
Detector resolution: 10.0000 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
dtprofit.ref scans | h = −15→15 |
Absorption correction: numerical NUMABS; Higashi, 2002 | k = −24→24 |
Tmin = 0.893, Tmax = 0.971 | l = −26→26 |
105320 measured reflections |
Refinement on F2 | Secondary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.133 | w = 1/[σ2(Fo2) + (0.0791P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
10363 reflections | Δρmax = 0.67 e Å−3 |
569 parameters | Δρmin = −0.31 e Å−3 |
0 restraints | Absolute structure: Flack x determined using 3169 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (3) |
C19H25N2OS+·C4H3O4− | V = 4544.7 (3) Å3 |
Mr = 444.53 | Z = 8 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 11.6395 (5) Å | µ = 0.18 mm−1 |
b = 19.0487 (6) Å | T = 103 K |
c = 20.4977 (7) Å | 0.5 × 0.3 × 0.2 mm |
R-AXIS RAPID diffractometer | 10363 independent reflections |
Absorption correction: numerical NUMABS; Higashi, 2002 | 8459 reflections with I > 2σ(I) |
Tmin = 0.893, Tmax = 0.971 | Rint = 0.085 |
105320 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.133 | Δρmax = 0.67 e Å−3 |
S = 1.05 | Δρmin = −0.31 e Å−3 |
10363 reflections | Absolute structure: Flack x determined using 3169 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013 |
569 parameters | Absolute structure parameter: −0.02 (3) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
S7 | 0.71907 (8) | 0.43498 (5) | 0.42513 (4) | 0.0376 (2) | |
S37 | 0.27962 (8) | 0.47770 (4) | 0.44305 (4) | 0.0324 (2) | |
O3 | 0.2810 (2) | 0.85941 (11) | 0.69965 (12) | 0.0340 (5) | |
O4 | 0.4194 (2) | 0.77876 (12) | 0.69694 (13) | 0.0380 (6) | |
O5 | 0.2773 (2) | 0.64259 (12) | 0.29296 (13) | 0.0395 (6) | |
O1 | 0.3156 (3) | 0.56393 (12) | 0.65973 (14) | 0.0458 (7) | |
O2 | 0.4351 (2) | 0.65270 (12) | 0.67442 (14) | 0.0397 (6) | |
H2O | 0.4307 | 0.6961 | 0.6812 | 0.048* | |
O22 | 0.3315 (2) | 0.23474 (12) | 0.42581 (12) | 0.0367 (6) | |
O7 | 0.3143 (3) | 0.93613 (13) | 0.33972 (16) | 0.0521 (8) | |
O6 | 0.4133 (2) | 0.72465 (13) | 0.28657 (14) | 0.0428 (6) | |
N48 | 0.0515 (2) | 0.44623 (13) | 0.75804 (13) | 0.0267 (6) | |
H48N | 0.1129 | 0.4098 | 0.7628 | 0.032* | |
N18 | 0.5491 (2) | 0.45179 (13) | 0.77062 (12) | 0.0261 (6) | |
H18N | 0.6141 | 0.4180 | 0.7763 | 0.031* | |
O8 | 0.4289 (2) | 0.85049 (13) | 0.30770 (15) | 0.0441 (6) | |
H8O | 0.4253 | 0.8067 | 0.3030 | 0.053* | |
N10 | 0.5392 (2) | 0.43086 (14) | 0.52619 (13) | 0.0274 (6) | |
C16 | 0.5607 (3) | 0.44213 (16) | 0.64667 (14) | 0.0256 (6) | |
H16 | 0.5808 | 0.4929 | 0.6417 | 0.031* | |
C20 | 0.4693 (3) | 0.4429 (2) | 0.82668 (16) | 0.0351 (8) | |
H20A | 0.4062 | 0.4767 | 0.8230 | 0.053* | |
H20B | 0.5110 | 0.4509 | 0.8675 | 0.053* | |
H20C | 0.4380 | 0.3951 | 0.8264 | 0.053* | |
C27 | 0.3141 (3) | 0.79688 (17) | 0.69359 (16) | 0.0304 (7) | |
C17 | 0.4879 (3) | 0.43375 (17) | 0.70818 (14) | 0.0269 (6) | |
H17A | 0.4192 | 0.4641 | 0.7042 | 0.032* | |
H17B | 0.4611 | 0.3845 | 0.7108 | 0.032* | |
N40 | 0.0636 (3) | 0.45554 (14) | 0.51572 (13) | 0.0327 (6) | |
C36 | 0.1707 (3) | 0.41769 (16) | 0.42030 (15) | 0.0288 (7) | |
C46 | 0.0698 (3) | 0.44388 (16) | 0.63495 (15) | 0.0291 (7) | |
H46 | 0.1011 | 0.4928 | 0.6358 | 0.035* | |
C45 | −0.0030 (3) | 0.43515 (18) | 0.57258 (16) | 0.0331 (7) | |
H45A | −0.0276 | 0.3856 | 0.5682 | 0.040* | |
H45B | −0.0727 | 0.4647 | 0.5756 | 0.040* | |
C47 | −0.0078 (3) | 0.43418 (17) | 0.69381 (16) | 0.0290 (7) | |
H47A | −0.0733 | 0.4671 | 0.6902 | 0.035* | |
H47B | −0.0391 | 0.3859 | 0.6932 | 0.035* | |
C50 | −0.0309 (3) | 0.4373 (2) | 0.81310 (17) | 0.0358 (8) | |
H50A | 0.0107 | 0.4396 | 0.8546 | 0.054* | |
H50B | −0.0691 | 0.3917 | 0.8093 | 0.054* | |
H50C | −0.0885 | 0.4748 | 0.8116 | 0.054* | |
C14 | 0.5155 (3) | 0.55931 (18) | 0.53450 (17) | 0.0339 (7) | |
H14 | 0.4561 | 0.5537 | 0.5659 | 0.041* | |
C21 | 0.6714 (3) | 0.39977 (18) | 0.64729 (17) | 0.0327 (7) | |
H21A | 0.7201 | 0.4156 | 0.6834 | 0.049* | |
H21B | 0.7121 | 0.4065 | 0.6059 | 0.049* | |
H21C | 0.6532 | 0.3499 | 0.6529 | 0.049* | |
O52 | −0.0838 (3) | 0.27161 (18) | 0.38223 (15) | 0.0592 (9) | |
C15 | 0.4825 (3) | 0.42064 (17) | 0.58918 (14) | 0.0270 (7) | |
H15A | 0.4609 | 0.3706 | 0.5939 | 0.032* | |
H15B | 0.4112 | 0.4489 | 0.5905 | 0.032* | |
C1 | 0.5213 (3) | 0.38102 (15) | 0.47535 (15) | 0.0264 (6) | |
C9 | 0.5686 (3) | 0.50069 (17) | 0.50747 (15) | 0.0299 (7) | |
C24 | 0.3317 (3) | 0.62659 (17) | 0.66822 (18) | 0.0341 (8) | |
C54 | 0.3118 (3) | 0.70422 (17) | 0.30093 (18) | 0.0347 (8) | |
C33 | 0.0037 (3) | 0.31867 (17) | 0.39121 (17) | 0.0332 (7) | |
C19 | 0.5978 (3) | 0.52445 (17) | 0.76919 (17) | 0.0339 (8) | |
H19A | 0.5370 | 0.5580 | 0.7580 | 0.051* | |
H19B | 0.6589 | 0.5269 | 0.7364 | 0.051* | |
H19C | 0.6293 | 0.5361 | 0.8122 | 0.051* | |
C3 | 0.4162 (3) | 0.28458 (16) | 0.42653 (17) | 0.0319 (7) | |
C26 | 0.2222 (3) | 0.74344 (17) | 0.68253 (19) | 0.0366 (8) | |
H26 | 0.1462 | 0.7617 | 0.6829 | 0.044* | |
C6 | 0.5962 (3) | 0.38091 (17) | 0.42268 (17) | 0.0313 (7) | |
C55 | 0.2258 (4) | 0.75469 (18) | 0.32921 (19) | 0.0401 (8) | |
H55 | 0.1546 | 0.7342 | 0.3416 | 0.048* | |
C57 | 0.3310 (3) | 0.87372 (18) | 0.32830 (18) | 0.0358 (8) | |
C39 | 0.0910 (3) | 0.52782 (18) | 0.50652 (17) | 0.0362 (8) | |
C31 | 0.0745 (3) | 0.41109 (16) | 0.46133 (15) | 0.0283 (7) | |
C8 | 0.6538 (3) | 0.51034 (18) | 0.46007 (16) | 0.0325 (7) | |
C4 | 0.4893 (4) | 0.28620 (18) | 0.37300 (18) | 0.0378 (8) | |
H4 | 0.4784 | 0.2541 | 0.3380 | 0.045* | |
C34 | 0.0976 (3) | 0.32530 (18) | 0.35056 (17) | 0.0345 (8) | |
H34 | 0.1053 | 0.2961 | 0.3132 | 0.041* | |
C5 | 0.5772 (3) | 0.33408 (18) | 0.37057 (17) | 0.0360 (8) | |
H5 | 0.6259 | 0.3357 | 0.3334 | 0.043* | |
C38 | 0.1890 (3) | 0.54566 (17) | 0.47043 (16) | 0.0348 (8) | |
C13 | 0.5500 (4) | 0.62664 (18) | 0.51517 (19) | 0.0444 (10) | |
H13 | 0.5144 | 0.6667 | 0.5340 | 0.053* | |
C2 | 0.4303 (3) | 0.33317 (16) | 0.47697 (16) | 0.0294 (7) | |
H2 | 0.3779 | 0.3337 | 0.5125 | 0.035* | |
C25 | 0.2291 (3) | 0.67395 (17) | 0.67218 (18) | 0.0360 (8) | |
H25 | 0.1572 | 0.6511 | 0.6664 | 0.043* | |
C51 | 0.1706 (3) | 0.3927 (2) | 0.63410 (19) | 0.0381 (8) | |
H51A | 0.2198 | 0.4014 | 0.6720 | 0.057* | |
H51B | 0.2151 | 0.3994 | 0.5940 | 0.057* | |
H51C | 0.1415 | 0.3445 | 0.6357 | 0.057* | |
C56 | 0.2338 (3) | 0.82429 (18) | 0.33969 (19) | 0.0391 (8) | |
H56 | 0.1666 | 0.8453 | 0.3572 | 0.047* | |
C32 | −0.0088 (3) | 0.36124 (17) | 0.44602 (17) | 0.0327 (7) | |
H32 | −0.0746 | 0.3563 | 0.4731 | 0.039* | |
C23 | 0.2465 (3) | 0.23796 (17) | 0.47604 (18) | 0.0347 (8) | |
H23A | 0.2832 | 0.2313 | 0.5186 | 0.052* | |
H23B | 0.1894 | 0.2009 | 0.4690 | 0.052* | |
H23C | 0.2085 | 0.2839 | 0.4749 | 0.052* | |
C49 | 0.1073 (3) | 0.51674 (18) | 0.76233 (18) | 0.0363 (8) | |
H49A | 0.0502 | 0.5533 | 0.7534 | 0.054* | |
H49B | 0.1694 | 0.5197 | 0.7302 | 0.054* | |
H49C | 0.1388 | 0.5234 | 0.8062 | 0.054* | |
C35 | 0.1809 (3) | 0.37539 (17) | 0.36501 (16) | 0.0323 (7) | |
H35 | 0.2453 | 0.3808 | 0.3370 | 0.039* | |
C12 | 0.6355 (4) | 0.6354 (2) | 0.46897 (19) | 0.0477 (10) | |
H12 | 0.6589 | 0.6812 | 0.4564 | 0.057* | |
C11 | 0.6869 (4) | 0.5769 (2) | 0.44106 (18) | 0.0433 (9) | |
H11 | 0.7448 | 0.5827 | 0.4089 | 0.052* | |
C42 | 0.1473 (6) | 0.6686 (2) | 0.4844 (2) | 0.0651 (15) | |
H42 | 0.1664 | 0.7163 | 0.4767 | 0.078* | |
C43 | 0.0522 (5) | 0.6517 (2) | 0.5214 (2) | 0.0640 (14) | |
H43 | 0.0068 | 0.6880 | 0.5399 | 0.077* | |
C44 | 0.0220 (4) | 0.5815 (2) | 0.5320 (2) | 0.0522 (11) | |
H44 | −0.0450 | 0.5703 | 0.5564 | 0.063* | |
C41 | 0.2149 (5) | 0.61537 (18) | 0.45858 (19) | 0.0482 (10) | |
H41 | 0.2796 | 0.6270 | 0.4325 | 0.058* | |
C53 | −0.1196 (4) | 0.2632 (2) | 0.3167 (2) | 0.0514 (10) | |
H53A | −0.1352 | 0.3093 | 0.2975 | 0.077* | |
H53B | −0.1896 | 0.2346 | 0.3154 | 0.077* | |
H53C | −0.0588 | 0.2397 | 0.2918 | 0.077* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S7 | 0.0263 (4) | 0.0496 (5) | 0.0369 (4) | 0.0003 (4) | 0.0064 (4) | 0.0061 (4) |
S37 | 0.0307 (4) | 0.0340 (4) | 0.0325 (4) | −0.0046 (3) | −0.0002 (4) | 0.0012 (3) |
O3 | 0.0333 (13) | 0.0272 (11) | 0.0415 (13) | 0.0013 (10) | −0.0098 (11) | 0.0008 (9) |
O4 | 0.0258 (13) | 0.0347 (12) | 0.0535 (16) | −0.0009 (10) | −0.0049 (11) | 0.0017 (11) |
O5 | 0.0373 (14) | 0.0298 (12) | 0.0513 (15) | −0.0017 (11) | 0.0075 (13) | −0.0054 (10) |
O1 | 0.0445 (17) | 0.0293 (13) | 0.0636 (17) | 0.0004 (11) | 0.0159 (13) | −0.0005 (12) |
O2 | 0.0287 (14) | 0.0324 (12) | 0.0581 (17) | 0.0044 (10) | 0.0049 (12) | −0.0010 (11) |
O22 | 0.0408 (15) | 0.0330 (11) | 0.0362 (13) | −0.0048 (11) | −0.0023 (11) | −0.0072 (10) |
O7 | 0.0460 (18) | 0.0310 (13) | 0.079 (2) | −0.0045 (12) | −0.0112 (15) | −0.0009 (13) |
O6 | 0.0294 (14) | 0.0404 (13) | 0.0586 (17) | −0.0002 (11) | 0.0101 (13) | −0.0012 (12) |
N48 | 0.0252 (14) | 0.0248 (12) | 0.0302 (13) | −0.0022 (11) | 0.0021 (11) | 0.0001 (10) |
N18 | 0.0259 (14) | 0.0291 (13) | 0.0234 (12) | 0.0003 (11) | −0.0018 (11) | −0.0038 (10) |
O8 | 0.0327 (15) | 0.0389 (13) | 0.0608 (18) | −0.0084 (11) | 0.0039 (13) | 0.0008 (13) |
N10 | 0.0279 (15) | 0.0328 (13) | 0.0214 (12) | −0.0046 (11) | 0.0011 (11) | −0.0005 (11) |
C16 | 0.0224 (16) | 0.0298 (15) | 0.0246 (14) | −0.0028 (13) | −0.0001 (12) | −0.0016 (12) |
C20 | 0.037 (2) | 0.0455 (19) | 0.0231 (16) | −0.0010 (16) | 0.0044 (13) | −0.0042 (14) |
C27 | 0.0304 (19) | 0.0321 (16) | 0.0288 (16) | −0.0012 (13) | −0.0072 (13) | 0.0050 (13) |
C17 | 0.0237 (16) | 0.0325 (15) | 0.0245 (15) | −0.0044 (13) | −0.0020 (12) | −0.0029 (12) |
N40 | 0.0352 (17) | 0.0339 (14) | 0.0289 (14) | −0.0013 (12) | 0.0042 (12) | −0.0038 (11) |
C36 | 0.0308 (17) | 0.0317 (15) | 0.0238 (15) | 0.0024 (13) | −0.0029 (13) | 0.0042 (12) |
C46 | 0.0240 (17) | 0.0308 (15) | 0.0324 (16) | −0.0022 (13) | 0.0021 (13) | −0.0014 (13) |
C45 | 0.0303 (18) | 0.0381 (16) | 0.0309 (17) | −0.0026 (14) | 0.0018 (14) | −0.0013 (14) |
C47 | 0.0219 (15) | 0.0326 (15) | 0.0325 (16) | −0.0027 (13) | −0.0013 (13) | 0.0000 (13) |
C50 | 0.0325 (19) | 0.0436 (19) | 0.0312 (17) | −0.0068 (15) | 0.0048 (14) | 0.0007 (15) |
C14 | 0.037 (2) | 0.0341 (16) | 0.0305 (17) | −0.0053 (15) | −0.0017 (14) | 0.0002 (14) |
C21 | 0.0250 (17) | 0.0432 (18) | 0.0297 (17) | 0.0027 (14) | −0.0025 (14) | −0.0052 (14) |
O52 | 0.060 (2) | 0.0741 (19) | 0.0432 (16) | −0.0270 (17) | −0.0057 (15) | −0.0035 (14) |
C15 | 0.0255 (17) | 0.0344 (15) | 0.0210 (15) | −0.0042 (13) | 0.0027 (12) | −0.0017 (12) |
C1 | 0.0275 (17) | 0.0288 (15) | 0.0228 (15) | 0.0044 (12) | −0.0012 (12) | −0.0008 (12) |
C9 | 0.0267 (17) | 0.0370 (17) | 0.0259 (15) | −0.0075 (14) | −0.0056 (13) | 0.0028 (13) |
C24 | 0.036 (2) | 0.0293 (16) | 0.0374 (19) | 0.0021 (14) | 0.0060 (15) | 0.0043 (14) |
C54 | 0.031 (2) | 0.0356 (18) | 0.0371 (19) | 0.0005 (14) | 0.0047 (15) | 0.0014 (14) |
C33 | 0.0325 (19) | 0.0354 (17) | 0.0316 (17) | −0.0067 (15) | −0.0037 (15) | 0.0030 (14) |
C19 | 0.039 (2) | 0.0303 (16) | 0.0319 (17) | −0.0043 (15) | −0.0036 (14) | −0.0055 (14) |
C3 | 0.0346 (19) | 0.0288 (15) | 0.0321 (17) | 0.0013 (13) | −0.0033 (15) | −0.0018 (13) |
C26 | 0.0250 (17) | 0.0302 (16) | 0.055 (2) | 0.0010 (14) | −0.0056 (17) | 0.0003 (14) |
C6 | 0.0275 (17) | 0.0351 (16) | 0.0313 (17) | 0.0073 (13) | 0.0022 (14) | 0.0022 (13) |
C55 | 0.030 (2) | 0.0370 (18) | 0.053 (2) | −0.0032 (15) | 0.0113 (18) | −0.0049 (15) |
C57 | 0.035 (2) | 0.0315 (17) | 0.041 (2) | −0.0039 (15) | −0.0073 (16) | 0.0028 (14) |
C39 | 0.045 (2) | 0.0327 (17) | 0.0311 (17) | 0.0061 (15) | −0.0009 (15) | −0.0005 (14) |
C31 | 0.0281 (18) | 0.0297 (15) | 0.0270 (16) | 0.0018 (13) | −0.0033 (13) | 0.0018 (12) |
C8 | 0.0283 (18) | 0.0422 (18) | 0.0269 (16) | −0.0073 (14) | −0.0021 (13) | 0.0046 (13) |
C4 | 0.046 (2) | 0.0362 (18) | 0.0314 (18) | 0.0051 (16) | 0.0009 (16) | −0.0069 (14) |
C34 | 0.043 (2) | 0.0328 (16) | 0.0275 (16) | −0.0044 (15) | −0.0001 (15) | −0.0009 (13) |
C5 | 0.038 (2) | 0.0404 (18) | 0.0295 (17) | 0.0089 (15) | 0.0084 (15) | −0.0010 (14) |
C38 | 0.047 (2) | 0.0311 (16) | 0.0264 (16) | −0.0013 (15) | −0.0032 (15) | 0.0021 (13) |
C13 | 0.065 (3) | 0.0323 (17) | 0.036 (2) | −0.0061 (18) | −0.0023 (19) | −0.0037 (15) |
C2 | 0.0294 (18) | 0.0313 (15) | 0.0276 (16) | 0.0034 (13) | −0.0006 (14) | −0.0029 (13) |
C25 | 0.0261 (18) | 0.0308 (16) | 0.051 (2) | −0.0015 (14) | −0.0002 (17) | 0.0022 (14) |
C51 | 0.0250 (18) | 0.048 (2) | 0.041 (2) | 0.0015 (15) | 0.0041 (16) | −0.0017 (16) |
C56 | 0.033 (2) | 0.0351 (17) | 0.050 (2) | 0.0008 (15) | 0.0056 (17) | −0.0034 (15) |
C32 | 0.0249 (17) | 0.0408 (17) | 0.0324 (17) | −0.0003 (14) | −0.0015 (14) | 0.0001 (14) |
C23 | 0.036 (2) | 0.0326 (16) | 0.0355 (18) | −0.0058 (14) | −0.0015 (15) | −0.0003 (14) |
C49 | 0.039 (2) | 0.0307 (17) | 0.0396 (19) | −0.0105 (15) | −0.0014 (15) | −0.0005 (14) |
C35 | 0.0341 (19) | 0.0342 (16) | 0.0286 (17) | −0.0003 (14) | 0.0033 (14) | 0.0031 (13) |
C12 | 0.068 (3) | 0.040 (2) | 0.035 (2) | −0.0235 (19) | −0.004 (2) | 0.0051 (16) |
C11 | 0.050 (2) | 0.049 (2) | 0.0305 (18) | −0.0188 (17) | −0.0003 (16) | 0.0023 (16) |
C42 | 0.117 (5) | 0.0329 (19) | 0.045 (2) | 0.002 (2) | 0.008 (3) | −0.0007 (18) |
C43 | 0.100 (4) | 0.039 (2) | 0.053 (3) | 0.019 (2) | 0.015 (3) | −0.0016 (19) |
C44 | 0.064 (3) | 0.047 (2) | 0.046 (2) | 0.009 (2) | 0.008 (2) | −0.0054 (18) |
C41 | 0.074 (3) | 0.0338 (18) | 0.037 (2) | −0.0100 (19) | 0.005 (2) | 0.0015 (15) |
C53 | 0.052 (3) | 0.060 (2) | 0.043 (2) | −0.013 (2) | −0.0028 (19) | −0.0103 (19) |
S7—C6 | 1.763 (4) | O52—C53 | 1.416 (5) |
S7—C8 | 1.775 (4) | C15—H15A | 0.9900 |
S37—C38 | 1.761 (4) | C15—H15B | 0.9900 |
S37—C36 | 1.769 (4) | C1—C6 | 1.388 (5) |
O3—C27 | 1.258 (4) | C1—C2 | 1.398 (5) |
O4—C27 | 1.276 (4) | C9—C8 | 1.401 (5) |
O5—C54 | 1.252 (4) | C24—C25 | 1.499 (5) |
O1—C24 | 1.221 (4) | C54—C55 | 1.504 (5) |
O2—C24 | 1.309 (5) | C33—C34 | 1.380 (5) |
O2—H2O | 0.8400 | C33—C32 | 1.393 (5) |
O22—C3 | 1.369 (4) | C19—H19A | 0.9800 |
O22—C23 | 1.429 (4) | C19—H19B | 0.9800 |
O7—C57 | 1.227 (4) | C19—H19C | 0.9800 |
O6—C54 | 1.277 (4) | C3—C4 | 1.389 (5) |
N48—C50 | 1.491 (4) | C3—C2 | 1.397 (5) |
N48—C49 | 1.494 (4) | C26—C25 | 1.343 (5) |
N48—C47 | 1.504 (4) | C26—H26 | 0.9500 |
N48—H48N | 1.0000 | C6—C5 | 1.409 (5) |
N18—C20 | 1.487 (4) | C55—C56 | 1.346 (5) |
N18—C19 | 1.496 (4) | C55—H55 | 0.9500 |
N18—C17 | 1.504 (4) | C57—C56 | 1.490 (5) |
N18—H18N | 1.0000 | C39—C38 | 1.401 (5) |
O8—C57 | 1.293 (5) | C39—C44 | 1.402 (5) |
O8—H8O | 0.8400 | C31—C32 | 1.393 (5) |
N10—C1 | 1.425 (4) | C8—C11 | 1.382 (5) |
N10—C9 | 1.426 (4) | C4—C5 | 1.372 (5) |
N10—C15 | 1.463 (4) | C4—H4 | 0.9500 |
C16—C21 | 1.520 (5) | C34—C35 | 1.392 (5) |
C16—C17 | 1.527 (4) | C34—H34 | 0.9500 |
C16—C15 | 1.544 (4) | C5—H5 | 0.9500 |
C16—H16 | 1.0000 | C38—C41 | 1.383 (5) |
C20—H20A | 0.9800 | C13—C12 | 1.383 (6) |
C20—H20B | 0.9800 | C13—H13 | 0.9500 |
C20—H20C | 0.9800 | C2—H2 | 0.9500 |
C27—C26 | 1.494 (5) | C25—H25 | 0.9500 |
C17—H17A | 0.9900 | C51—H51A | 0.9800 |
C17—H17B | 0.9900 | C51—H51B | 0.9800 |
N40—C31 | 1.406 (4) | C51—H51C | 0.9800 |
N40—C39 | 1.426 (4) | C56—H56 | 0.9500 |
N40—C45 | 1.453 (4) | C32—H32 | 0.9500 |
C36—C35 | 1.396 (5) | C23—H23A | 0.9800 |
C36—C31 | 1.406 (5) | C23—H23B | 0.9800 |
C46—C47 | 1.519 (4) | C23—H23C | 0.9800 |
C46—C51 | 1.525 (5) | C49—H49A | 0.9800 |
C46—C45 | 1.543 (5) | C49—H49B | 0.9800 |
C46—H46 | 1.0000 | C49—H49C | 0.9800 |
C45—H45A | 0.9900 | C35—H35 | 0.9500 |
C45—H45B | 0.9900 | C12—C11 | 1.387 (6) |
C47—H47A | 0.9900 | C12—H12 | 0.9500 |
C47—H47B | 0.9900 | C11—H11 | 0.9500 |
C50—H50A | 0.9800 | C42—C43 | 1.379 (8) |
C50—H50B | 0.9800 | C42—C41 | 1.388 (7) |
C50—H50C | 0.9800 | C42—H42 | 0.9500 |
C14—C9 | 1.391 (5) | C43—C44 | 1.399 (6) |
C14—C13 | 1.401 (5) | C43—H43 | 0.9500 |
C14—H14 | 0.9500 | C44—H44 | 0.9500 |
C21—H21A | 0.9800 | C41—H41 | 0.9500 |
C21—H21B | 0.9800 | C53—H53A | 0.9800 |
C21—H21C | 0.9800 | C53—H53B | 0.9800 |
O52—C33 | 1.369 (4) | C53—H53C | 0.9800 |
C6—S7—C8 | 97.88 (16) | N18—C19—H19A | 109.5 |
C38—S37—C36 | 97.47 (17) | N18—C19—H19B | 109.5 |
C24—O2—H2O | 109.5 | H19A—C19—H19B | 109.5 |
C3—O22—C23 | 117.5 (2) | N18—C19—H19C | 109.5 |
C50—N48—C49 | 109.7 (3) | H19A—C19—H19C | 109.5 |
C50—N48—C47 | 110.5 (3) | H19B—C19—H19C | 109.5 |
C49—N48—C47 | 112.8 (2) | O22—C3—C4 | 116.6 (3) |
C50—N48—H48N | 107.9 | O22—C3—C2 | 123.5 (3) |
C49—N48—H48N | 107.9 | C4—C3—C2 | 119.9 (3) |
C47—N48—H48N | 107.9 | C25—C26—C27 | 130.8 (3) |
C20—N18—C19 | 110.9 (3) | C25—C26—H26 | 114.6 |
C20—N18—C17 | 109.6 (3) | C27—C26—H26 | 114.6 |
C19—N18—C17 | 112.0 (2) | C1—C6—C5 | 119.5 (3) |
C20—N18—H18N | 108.1 | C1—C6—S7 | 119.1 (3) |
C19—N18—H18N | 108.1 | C5—C6—S7 | 121.2 (3) |
C17—N18—H18N | 108.1 | C56—C55—C54 | 130.1 (4) |
C57—O8—H8O | 109.5 | C56—C55—H55 | 114.9 |
C1—N10—C9 | 117.4 (3) | C54—C55—H55 | 114.9 |
C1—N10—C15 | 119.4 (3) | O7—C57—O8 | 122.2 (3) |
C9—N10—C15 | 118.0 (3) | O7—C57—C56 | 117.5 (4) |
C21—C16—C17 | 114.1 (3) | O8—C57—C56 | 120.2 (3) |
C21—C16—C15 | 111.4 (3) | C38—C39—C44 | 119.1 (3) |
C17—C16—C15 | 106.0 (2) | C38—C39—N40 | 119.1 (3) |
C21—C16—H16 | 108.4 | C44—C39—N40 | 121.7 (4) |
C17—C16—H16 | 108.4 | C32—C31—N40 | 121.7 (3) |
C15—C16—H16 | 108.4 | C32—C31—C36 | 118.7 (3) |
N18—C20—H20A | 109.5 | N40—C31—C36 | 119.5 (3) |
N18—C20—H20B | 109.5 | C11—C8—C9 | 120.9 (3) |
H20A—C20—H20B | 109.5 | C11—C8—S7 | 120.6 (3) |
N18—C20—H20C | 109.5 | C9—C8—S7 | 118.5 (3) |
H20A—C20—H20C | 109.5 | C5—C4—C3 | 120.0 (3) |
H20B—C20—H20C | 109.5 | C5—C4—H4 | 120.0 |
O3—C27—O4 | 123.0 (3) | C3—C4—H4 | 120.0 |
O3—C27—C26 | 116.2 (3) | C33—C34—C35 | 119.1 (3) |
O4—C27—C26 | 120.8 (3) | C33—C34—H34 | 120.5 |
N18—C17—C16 | 114.6 (3) | C35—C34—H34 | 120.5 |
N18—C17—H17A | 108.6 | C4—C5—C6 | 120.7 (3) |
C16—C17—H17A | 108.6 | C4—C5—H5 | 119.7 |
N18—C17—H17B | 108.6 | C6—C5—H5 | 119.7 |
C16—C17—H17B | 108.6 | C41—C38—C39 | 120.2 (4) |
H17A—C17—H17B | 107.6 | C41—C38—S37 | 121.3 (3) |
C31—N40—C39 | 117.2 (3) | C39—C38—S37 | 118.5 (2) |
C31—N40—C45 | 121.6 (3) | C12—C13—C14 | 120.7 (4) |
C39—N40—C45 | 118.9 (3) | C12—C13—H13 | 119.7 |
C35—C36—C31 | 120.1 (3) | C14—C13—H13 | 119.7 |
C35—C36—S37 | 121.7 (3) | C3—C2—C1 | 120.2 (3) |
C31—C36—S37 | 118.1 (2) | C3—C2—H2 | 119.9 |
C47—C46—C51 | 112.9 (3) | C1—C2—H2 | 119.9 |
C47—C46—C45 | 108.6 (3) | C26—C25—C24 | 130.5 (3) |
C51—C46—C45 | 110.1 (3) | C26—C25—H25 | 114.8 |
C47—C46—H46 | 108.4 | C24—C25—H25 | 114.8 |
C51—C46—H46 | 108.4 | C46—C51—H51A | 109.5 |
C45—C46—H46 | 108.4 | C46—C51—H51B | 109.5 |
N40—C45—C46 | 110.0 (3) | H51A—C51—H51B | 109.5 |
N40—C45—H45A | 109.7 | C46—C51—H51C | 109.5 |
C46—C45—H45A | 109.7 | H51A—C51—H51C | 109.5 |
N40—C45—H45B | 109.7 | H51B—C51—H51C | 109.5 |
C46—C45—H45B | 109.7 | C55—C56—C57 | 130.5 (4) |
H45A—C45—H45B | 108.2 | C55—C56—H56 | 114.7 |
N48—C47—C46 | 113.8 (3) | C57—C56—H56 | 114.7 |
N48—C47—H47A | 108.8 | C33—C32—C31 | 120.4 (3) |
C46—C47—H47A | 108.8 | C33—C32—H32 | 119.8 |
N48—C47—H47B | 108.8 | C31—C32—H32 | 119.8 |
C46—C47—H47B | 108.8 | O22—C23—H23A | 109.5 |
H47A—C47—H47B | 107.7 | O22—C23—H23B | 109.5 |
N48—C50—H50A | 109.5 | H23A—C23—H23B | 109.5 |
N48—C50—H50B | 109.5 | O22—C23—H23C | 109.5 |
H50A—C50—H50B | 109.5 | H23A—C23—H23C | 109.5 |
N48—C50—H50C | 109.5 | H23B—C23—H23C | 109.5 |
H50A—C50—H50C | 109.5 | N48—C49—H49A | 109.5 |
H50B—C50—H50C | 109.5 | N48—C49—H49B | 109.5 |
C9—C14—C13 | 119.6 (3) | H49A—C49—H49B | 109.5 |
C9—C14—H14 | 120.2 | N48—C49—H49C | 109.5 |
C13—C14—H14 | 120.2 | H49A—C49—H49C | 109.5 |
C16—C21—H21A | 109.5 | H49B—C49—H49C | 109.5 |
C16—C21—H21B | 109.5 | C34—C35—C36 | 120.6 (3) |
H21A—C21—H21B | 109.5 | C34—C35—H35 | 119.7 |
C16—C21—H21C | 109.5 | C36—C35—H35 | 119.7 |
H21A—C21—H21C | 109.5 | C13—C12—C11 | 119.7 (3) |
H21B—C21—H21C | 109.5 | C13—C12—H12 | 120.1 |
C33—O52—C53 | 114.9 (3) | C11—C12—H12 | 120.1 |
N10—C15—C16 | 111.9 (3) | C8—C11—C12 | 120.0 (4) |
N10—C15—H15A | 109.2 | C8—C11—H11 | 120.0 |
C16—C15—H15A | 109.2 | C12—C11—H11 | 120.0 |
N10—C15—H15B | 109.2 | C43—C42—C41 | 119.6 (4) |
C16—C15—H15B | 109.2 | C43—C42—H42 | 120.2 |
H15A—C15—H15B | 107.9 | C41—C42—H42 | 120.2 |
C6—C1—C2 | 119.6 (3) | C42—C43—C44 | 120.7 (4) |
C6—C1—N10 | 118.6 (3) | C42—C43—H43 | 119.7 |
C2—C1—N10 | 121.9 (3) | C44—C43—H43 | 119.7 |
C14—C9—C8 | 119.1 (3) | C43—C44—C39 | 119.6 (4) |
C14—C9—N10 | 122.3 (3) | C43—C44—H44 | 120.2 |
C8—C9—N10 | 118.6 (3) | C39—C44—H44 | 120.2 |
O1—C24—O2 | 121.8 (3) | C38—C41—C42 | 120.7 (4) |
O1—C24—C25 | 118.3 (3) | C38—C41—H41 | 119.7 |
O2—C24—C25 | 119.9 (3) | C42—C41—H41 | 119.7 |
O5—C54—O6 | 123.5 (3) | O52—C53—H53A | 109.5 |
O5—C54—C55 | 115.8 (3) | O52—C53—H53B | 109.5 |
O6—C54—C55 | 120.6 (3) | H53A—C53—H53B | 109.5 |
O52—C33—C34 | 124.6 (3) | O52—C53—H53C | 109.5 |
O52—C33—C32 | 114.3 (3) | H53A—C53—H53C | 109.5 |
C34—C33—C32 | 121.1 (3) | H53B—C53—H53C | 109.5 |
Cg is the centroid of the C31–C36 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O4 | 0.84 | 1.61 | 2.452 (3) | 178 |
O8—H8O···O6 | 0.84 | 1.61 | 2.443 (4) | 174 |
N18—H18N···O3i | 1.00 | 1.73 | 2.716 (3) | 170 |
N48—H48N···O5ii | 1.00 | 1.74 | 2.710 (3) | 164 |
N48—H48N···O6ii | 1.00 | 2.63 | 3.332 (4) | 128 |
C11—H11···O3iii | 0.95 | 2.52 | 3.316 (5) | 141 |
C14—H14···O1 | 0.95 | 2.53 | 3.466 (5) | 167 |
C17—H17A···O1 | 0.99 | 2.43 | 3.340 (4) | 153 |
C19—H19B···O7iii | 0.99 | 2.49 | 3.449 (5) | 166 |
C23—H23A···O52iv | 0.98 | 2.56 | 3.518 (5) | 167 |
C23—H23C···Cg | 0.98 | 2.47 | 3.421 (4) | 145 |
C47—H47A···O7v | 0.99 | 2.34 | 3.296 (4) | 161 |
C49—H49B···O1 | 0.98 | 2.39 | 3.333 (5) | 163 |
C50—H50B···O3vi | 0.98 | 2.55 | 3.278 (4) | 131 |
C53—H53C···O4vii | 0.98 | 2.56 | 3.479 (5) | 156 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1/2, −y+1, z+1/2; (iii) x+1/2, −y+3/2, −z+1; (iv) x+1/2, −y+1/2, −z+1; (v) x−1/2, −y+3/2, −z+1; (vi) −x, y−1/2, −z+3/2; (vii) −x+1/2, −y+1, z−1/2. |
Cg is the centroid of the C31–C36 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O4 | 0.84 | 1.61 | 2.452 (3) | 178 |
O8—H8O···O6 | 0.84 | 1.61 | 2.443 (4) | 174 |
N18—H18N···O3i | 1.00 | 1.73 | 2.716 (3) | 170 |
N48—H48N···O5ii | 1.00 | 1.74 | 2.710 (3) | 164 |
N48—H48N···O6ii | 1.00 | 2.63 | 3.332 (4) | 128 |
C11—H11···O3iii | 0.95 | 2.52 | 3.316 (5) | 141 |
C14—H14···O1 | 0.95 | 2.53 | 3.466 (5) | 167 |
C17—H17A···O1 | 0.99 | 2.43 | 3.340 (4) | 153 |
C19—H19B···O7iii | 0.99 | 2.49 | 3.449 (5) | 166 |
C23—H23A···O52iv | 0.98 | 2.56 | 3.518 (5) | 167 |
C23—H23C···Cg | 0.98 | 2.47 | 3.421 (4) | 145 |
C47—H47A···O7v | 0.99 | 2.34 | 3.296 (4) | 161 |
C49—H49B···O1 | 0.98 | 2.39 | 3.333 (5) | 163 |
C50—H50B···O3vi | 0.98 | 2.55 | 3.278 (4) | 131 |
C53—H53C···O4vii | 0.98 | 2.56 | 3.479 (5) | 156 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1/2, −y+1, z+1/2; (iii) x+1/2, −y+3/2, −z+1; (iv) x+1/2, −y+1/2, −z+1; (v) x−1/2, −y+3/2, −z+1; (vi) −x, y−1/2, −z+3/2; (vii) −x+1/2, −y+1, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C19H25N2OS+·C4H3O4− |
Mr | 444.53 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 103 |
a, b, c (Å) | 11.6395 (5), 19.0487 (6), 20.4977 (7) |
V (Å3) | 4544.7 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.5 × 0.3 × 0.2 |
Data collection | |
Diffractometer | R-AXIS RAPID |
Absorption correction | Numerical NUMABS; Higashi, 2002 |
Tmin, Tmax | 0.893, 0.971 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 105320, 10363, 8459 |
Rint | 0.085 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.133, 1.05 |
No. of reflections | 10363 |
No. of parameters | 569 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −0.31 |
Absolute structure | Flack x determined using 3169 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013 |
Absolute structure parameter | −0.02 (3) |
Computer programs: CrystalClear (Rigaku/MSC, 2007), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), Mercury (Macrae et al., 2006) and PLATON (Spek, 2009).
Acknowledgements
This work was supported financially by the Hungarian Scientific Research Fund, project numbers OTKA K-115762 and K-100801. GTG is grateful for a Junior Research Fellowship (No. 255512109) for financial support.
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