research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 72| Part 5| May 2016| Pages 612-615

Crystal structure of levomepromazine maleate

CROSSMARK_Color_square_no_text.svg

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

Edited by M. Gdaniec, Adam Mickiewicz University, Poland (Received 27 December 2015; accepted 23 March 2016; online 5 April 2016)

The asymmetric unit of the title salt, C19H25N2OS+·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.

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[Froimowitz, M. & Cody, V. (1993). J. Med. Chem. 36, 2219-2227.]). 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 crystal structure of neutral (R)-levomepromazine has been reported previously, including the determination of its absolute configuration (Sato et al.). As (R)-levomepromazine is generally sold in the form of its maleate salt, we report here the crystal structure of this compound and compare the conformation of neutral levomepromazine with those of its cationic forms.

[Scheme 1]

2. Structural commentary

The asymmetric unit of the title compound comprises two levomepromazine cations and two hydrogen maleate anions (Fig. 1[link]). 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. 2[link]a 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[Sato, M., Miki, K., Tanaka, N., Kasai, N., Ishimaru, T. & Munakata, T. (1980). Acta Cryst. B36, 2176-2178.]) and 43.09° at 121 K (Dahl et al., 1982[Dahl, S. G., Hjorth, M. & Hough, E. (1982). Mol. Pharmacol. 21, 409-414.])].

[Figure 1]
Figure 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.
[Figure 2]
Figure 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).

The 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[Marsau, P. & Gauthier, J. (1973). Acta Cryst. B29, 992-998.]) (see Fig. 2[link]b). 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[link], Fig. 3[link]).

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C31–C36 ring.

D—H⋯A D—H H⋯A DA 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—H23CCg 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-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) [-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]; (iii) [x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]; (iv) [x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]; (v) [x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]; (vi) [-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (vii) [-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}].
[Figure 3]
Figure 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.

3. Supra­molecular features

The crystal structure of the title compound features strong N—H⋯O hydrogen bonds and several weak C—H⋯O inter­actions (Table 1[link]). The maleate anions form ionic pairs with the protonated amino groups of the levomepromazine cations by strong N—H⋯O inter­actions (Fig. 3[link]). 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—H23CCg(C31–C36), Table 1[link]]. 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[link]). 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[link], Fig. 4[link]).

[Figure 4]
Figure 4
Crystal packing along the bc plane showing the N—H⋯O and C—H⋯O inter­actions as turquoise lines.

4. 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 refinement are summarized in Table 2[link]. 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 absolute configuration around the C16 and C46 atoms in the title compound (Fig. 1[link]) were determined to be S from anomalous dispersion effects.

Table 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)
V3) 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[Higashi, T. (2002). NUMABS. Rigaku/MSC Inc., Tokyo, Japan.]
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−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[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.]
Absolute structure parameter −0.02 (3)
Computer programs: CrystalClear (Rigaku/MSC, 2007[Rigaku/MSC (2007). CrystalClear. Rigaku/MSC Inc., Tokyo, Japan.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Chemical context top

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 crystal structure of neutral (R)- levomepromazine has been reported previously, including the determination of its absolute configuration (Sato et al.). As (R)- levomepromazine is generally sold in the form of its maleate salt, we report here the crystal structure of this compound and compare the conformation of neutral levomepromazine with those of its cationic forms.

Structural commentary top

The asymmetric unit 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).

Supra­molecular features top

The crystal structure 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···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).

Synthesis and crystallization top

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.

Refinement top

Crystal data, data collection and details of the structure refinement 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 absolute configuration around the C16 and C46 atoms in the title compound (Fig. 1) were determined to be S from anomalous dispersion effects.

Structure description top

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 crystal structure of neutral (R)- levomepromazine has been reported previously, including the determination of its absolute configuration (Sato et al.). As (R)- levomepromazine is generally sold in the form of its maleate salt, we report here the crystal structure of this compound and compare the conformation of neutral levomepromazine with those of its cationic forms.

The asymmetric unit 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 crystal structure 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···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).

Synthesis and crystallization top

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.

Refinement details top

Crystal data, data collection and details of the structure refinement 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 absolute configuration around the C16 and C46 atoms in the title compound (Fig. 1) were determined to be S from anomalous dispersion effects.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2007); cell refinement: 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).

Figures top
[Figure 1] 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.
[Figure 2] 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).
[Figure 3] 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.
[Figure 4] Fig. 4. Crystal packing along the bc plane showing the N—H···O and C—H···O interactions in dashed lines.
(-)-(S)-3-(2-Methoxyphenothiazin-10-yl)-N,N,2-trimethylpropanaminium hydrogen maleate top
Crystal data top
C19H25N2OS+·C4H3O4Dx = 1.299 Mg m3
Mr = 444.53Melting point = 457–459 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
a = 11.6395 (5) ÅCell parameters from 74983 reflections
b = 19.0487 (6) Åθ = 3.2–27.5°
c = 20.4977 (7) ŵ = 0.18 mm1
V = 4544.7 (3) Å3T = 103 K
Z = 8Prism, colourless
F(000) = 18880.5 × 0.3 × 0.2 mm
Data collection top
R-AXIS RAPID
diffractometer
10363 independent reflections
Radiation source: NORMAL-focus sealed tube8459 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.085
Detector resolution: 10.0000 pixels mm-1θmax = 27.5°, θmin = 3.2°
dtprofit.ref scansh = 1515
Absorption correction: numerical
NUMABS; Higashi, 2002
k = 2424
Tmin = 0.893, Tmax = 0.971l = 2626
105320 measured reflections
Refinement top
Refinement on F2Secondary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049H-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 reflectionsΔρmax = 0.67 e Å3
569 parametersΔρmin = 0.31 e Å3
0 restraintsAbsolute structure: Flack x determined using 3169 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.02 (3)
Crystal data top
C19H25N2OS+·C4H3O4V = 4544.7 (3) Å3
Mr = 444.53Z = 8
Orthorhombic, P212121Mo Kα radiation
a = 11.6395 (5) ŵ = 0.18 mm1
b = 19.0487 (6) ÅT = 103 K
c = 20.4977 (7) Å0.5 × 0.3 × 0.2 mm
Data collection top
R-AXIS RAPID
diffractometer
10363 independent reflections
Absorption correction: numerical
NUMABS; Higashi, 2002
8459 reflections with I > 2σ(I)
Tmin = 0.893, Tmax = 0.971Rint = 0.085
105320 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.133Δρmax = 0.67 e Å3
S = 1.05Δρmin = 0.31 e Å3
10363 reflectionsAbsolute structure: Flack x determined using 3169 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013
569 parametersAbsolute structure parameter: 0.02 (3)
0 restraints
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
S70.71907 (8)0.43498 (5)0.42513 (4)0.0376 (2)
S370.27962 (8)0.47770 (4)0.44305 (4)0.0324 (2)
O30.2810 (2)0.85941 (11)0.69965 (12)0.0340 (5)
O40.4194 (2)0.77876 (12)0.69694 (13)0.0380 (6)
O50.2773 (2)0.64259 (12)0.29296 (13)0.0395 (6)
O10.3156 (3)0.56393 (12)0.65973 (14)0.0458 (7)
O20.4351 (2)0.65270 (12)0.67442 (14)0.0397 (6)
H2O0.43070.69610.68120.048*
O220.3315 (2)0.23474 (12)0.42581 (12)0.0367 (6)
O70.3143 (3)0.93613 (13)0.33972 (16)0.0521 (8)
O60.4133 (2)0.72465 (13)0.28657 (14)0.0428 (6)
N480.0515 (2)0.44623 (13)0.75804 (13)0.0267 (6)
H48N0.11290.40980.76280.032*
N180.5491 (2)0.45179 (13)0.77062 (12)0.0261 (6)
H18N0.61410.41800.77630.031*
O80.4289 (2)0.85049 (13)0.30770 (15)0.0441 (6)
H8O0.42530.80670.30300.053*
N100.5392 (2)0.43086 (14)0.52619 (13)0.0274 (6)
C160.5607 (3)0.44213 (16)0.64667 (14)0.0256 (6)
H160.58080.49290.64170.031*
C200.4693 (3)0.4429 (2)0.82668 (16)0.0351 (8)
H20A0.40620.47670.82300.053*
H20B0.51100.45090.86750.053*
H20C0.43800.39510.82640.053*
C270.3141 (3)0.79688 (17)0.69359 (16)0.0304 (7)
C170.4879 (3)0.43375 (17)0.70818 (14)0.0269 (6)
H17A0.41920.46410.70420.032*
H17B0.46110.38450.71080.032*
N400.0636 (3)0.45554 (14)0.51572 (13)0.0327 (6)
C360.1707 (3)0.41769 (16)0.42030 (15)0.0288 (7)
C460.0698 (3)0.44388 (16)0.63495 (15)0.0291 (7)
H460.10110.49280.63580.035*
C450.0030 (3)0.43515 (18)0.57258 (16)0.0331 (7)
H45A0.02760.38560.56820.040*
H45B0.07270.46470.57560.040*
C470.0078 (3)0.43418 (17)0.69381 (16)0.0290 (7)
H47A0.07330.46710.69020.035*
H47B0.03910.38590.69320.035*
C500.0309 (3)0.4373 (2)0.81310 (17)0.0358 (8)
H50A0.01070.43960.85460.054*
H50B0.06910.39170.80930.054*
H50C0.08850.47480.81160.054*
C140.5155 (3)0.55931 (18)0.53450 (17)0.0339 (7)
H140.45610.55370.56590.041*
C210.6714 (3)0.39977 (18)0.64729 (17)0.0327 (7)
H21A0.72010.41560.68340.049*
H21B0.71210.40650.60590.049*
H21C0.65320.34990.65290.049*
O520.0838 (3)0.27161 (18)0.38223 (15)0.0592 (9)
C150.4825 (3)0.42064 (17)0.58918 (14)0.0270 (7)
H15A0.46090.37060.59390.032*
H15B0.41120.44890.59050.032*
C10.5213 (3)0.38102 (15)0.47535 (15)0.0264 (6)
C90.5686 (3)0.50069 (17)0.50747 (15)0.0299 (7)
C240.3317 (3)0.62659 (17)0.66822 (18)0.0341 (8)
C540.3118 (3)0.70422 (17)0.30093 (18)0.0347 (8)
C330.0037 (3)0.31867 (17)0.39121 (17)0.0332 (7)
C190.5978 (3)0.52445 (17)0.76919 (17)0.0339 (8)
H19A0.53700.55800.75800.051*
H19B0.65890.52690.73640.051*
H19C0.62930.53610.81220.051*
C30.4162 (3)0.28458 (16)0.42653 (17)0.0319 (7)
C260.2222 (3)0.74344 (17)0.68253 (19)0.0366 (8)
H260.14620.76170.68290.044*
C60.5962 (3)0.38091 (17)0.42268 (17)0.0313 (7)
C550.2258 (4)0.75469 (18)0.32921 (19)0.0401 (8)
H550.15460.73420.34160.048*
C570.3310 (3)0.87372 (18)0.32830 (18)0.0358 (8)
C390.0910 (3)0.52782 (18)0.50652 (17)0.0362 (8)
C310.0745 (3)0.41109 (16)0.46133 (15)0.0283 (7)
C80.6538 (3)0.51034 (18)0.46007 (16)0.0325 (7)
C40.4893 (4)0.28620 (18)0.37300 (18)0.0378 (8)
H40.47840.25410.33800.045*
C340.0976 (3)0.32530 (18)0.35056 (17)0.0345 (8)
H340.10530.29610.31320.041*
C50.5772 (3)0.33408 (18)0.37057 (17)0.0360 (8)
H50.62590.33570.33340.043*
C380.1890 (3)0.54566 (17)0.47043 (16)0.0348 (8)
C130.5500 (4)0.62664 (18)0.51517 (19)0.0444 (10)
H130.51440.66670.53400.053*
C20.4303 (3)0.33317 (16)0.47697 (16)0.0294 (7)
H20.37790.33370.51250.035*
C250.2291 (3)0.67395 (17)0.67218 (18)0.0360 (8)
H250.15720.65110.66640.043*
C510.1706 (3)0.3927 (2)0.63410 (19)0.0381 (8)
H51A0.21980.40140.67200.057*
H51B0.21510.39940.59400.057*
H51C0.14150.34450.63570.057*
C560.2338 (3)0.82429 (18)0.33969 (19)0.0391 (8)
H560.16660.84530.35720.047*
C320.0088 (3)0.36124 (17)0.44602 (17)0.0327 (7)
H320.07460.35630.47310.039*
C230.2465 (3)0.23796 (17)0.47604 (18)0.0347 (8)
H23A0.28320.23130.51860.052*
H23B0.18940.20090.46900.052*
H23C0.20850.28390.47490.052*
C490.1073 (3)0.51674 (18)0.76233 (18)0.0363 (8)
H49A0.05020.55330.75340.054*
H49B0.16940.51970.73020.054*
H49C0.13880.52340.80620.054*
C350.1809 (3)0.37539 (17)0.36501 (16)0.0323 (7)
H350.24530.38080.33700.039*
C120.6355 (4)0.6354 (2)0.46897 (19)0.0477 (10)
H120.65890.68120.45640.057*
C110.6869 (4)0.5769 (2)0.44106 (18)0.0433 (9)
H110.74480.58270.40890.052*
C420.1473 (6)0.6686 (2)0.4844 (2)0.0651 (15)
H420.16640.71630.47670.078*
C430.0522 (5)0.6517 (2)0.5214 (2)0.0640 (14)
H430.00680.68800.53990.077*
C440.0220 (4)0.5815 (2)0.5320 (2)0.0522 (11)
H440.04500.57030.55640.063*
C410.2149 (5)0.61537 (18)0.45858 (19)0.0482 (10)
H410.27960.62700.43250.058*
C530.1196 (4)0.2632 (2)0.3167 (2)0.0514 (10)
H53A0.13520.30930.29750.077*
H53B0.18960.23460.31540.077*
H53C0.05880.23970.29180.077*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S70.0263 (4)0.0496 (5)0.0369 (4)0.0003 (4)0.0064 (4)0.0061 (4)
S370.0307 (4)0.0340 (4)0.0325 (4)0.0046 (3)0.0002 (4)0.0012 (3)
O30.0333 (13)0.0272 (11)0.0415 (13)0.0013 (10)0.0098 (11)0.0008 (9)
O40.0258 (13)0.0347 (12)0.0535 (16)0.0009 (10)0.0049 (11)0.0017 (11)
O50.0373 (14)0.0298 (12)0.0513 (15)0.0017 (11)0.0075 (13)0.0054 (10)
O10.0445 (17)0.0293 (13)0.0636 (17)0.0004 (11)0.0159 (13)0.0005 (12)
O20.0287 (14)0.0324 (12)0.0581 (17)0.0044 (10)0.0049 (12)0.0010 (11)
O220.0408 (15)0.0330 (11)0.0362 (13)0.0048 (11)0.0023 (11)0.0072 (10)
O70.0460 (18)0.0310 (13)0.079 (2)0.0045 (12)0.0112 (15)0.0009 (13)
O60.0294 (14)0.0404 (13)0.0586 (17)0.0002 (11)0.0101 (13)0.0012 (12)
N480.0252 (14)0.0248 (12)0.0302 (13)0.0022 (11)0.0021 (11)0.0001 (10)
N180.0259 (14)0.0291 (13)0.0234 (12)0.0003 (11)0.0018 (11)0.0038 (10)
O80.0327 (15)0.0389 (13)0.0608 (18)0.0084 (11)0.0039 (13)0.0008 (13)
N100.0279 (15)0.0328 (13)0.0214 (12)0.0046 (11)0.0011 (11)0.0005 (11)
C160.0224 (16)0.0298 (15)0.0246 (14)0.0028 (13)0.0001 (12)0.0016 (12)
C200.037 (2)0.0455 (19)0.0231 (16)0.0010 (16)0.0044 (13)0.0042 (14)
C270.0304 (19)0.0321 (16)0.0288 (16)0.0012 (13)0.0072 (13)0.0050 (13)
C170.0237 (16)0.0325 (15)0.0245 (15)0.0044 (13)0.0020 (12)0.0029 (12)
N400.0352 (17)0.0339 (14)0.0289 (14)0.0013 (12)0.0042 (12)0.0038 (11)
C360.0308 (17)0.0317 (15)0.0238 (15)0.0024 (13)0.0029 (13)0.0042 (12)
C460.0240 (17)0.0308 (15)0.0324 (16)0.0022 (13)0.0021 (13)0.0014 (13)
C450.0303 (18)0.0381 (16)0.0309 (17)0.0026 (14)0.0018 (14)0.0013 (14)
C470.0219 (15)0.0326 (15)0.0325 (16)0.0027 (13)0.0013 (13)0.0000 (13)
C500.0325 (19)0.0436 (19)0.0312 (17)0.0068 (15)0.0048 (14)0.0007 (15)
C140.037 (2)0.0341 (16)0.0305 (17)0.0053 (15)0.0017 (14)0.0002 (14)
C210.0250 (17)0.0432 (18)0.0297 (17)0.0027 (14)0.0025 (14)0.0052 (14)
O520.060 (2)0.0741 (19)0.0432 (16)0.0270 (17)0.0057 (15)0.0035 (14)
C150.0255 (17)0.0344 (15)0.0210 (15)0.0042 (13)0.0027 (12)0.0017 (12)
C10.0275 (17)0.0288 (15)0.0228 (15)0.0044 (12)0.0012 (12)0.0008 (12)
C90.0267 (17)0.0370 (17)0.0259 (15)0.0075 (14)0.0056 (13)0.0028 (13)
C240.036 (2)0.0293 (16)0.0374 (19)0.0021 (14)0.0060 (15)0.0043 (14)
C540.031 (2)0.0356 (18)0.0371 (19)0.0005 (14)0.0047 (15)0.0014 (14)
C330.0325 (19)0.0354 (17)0.0316 (17)0.0067 (15)0.0037 (15)0.0030 (14)
C190.039 (2)0.0303 (16)0.0319 (17)0.0043 (15)0.0036 (14)0.0055 (14)
C30.0346 (19)0.0288 (15)0.0321 (17)0.0013 (13)0.0033 (15)0.0018 (13)
C260.0250 (17)0.0302 (16)0.055 (2)0.0010 (14)0.0056 (17)0.0003 (14)
C60.0275 (17)0.0351 (16)0.0313 (17)0.0073 (13)0.0022 (14)0.0022 (13)
C550.030 (2)0.0370 (18)0.053 (2)0.0032 (15)0.0113 (18)0.0049 (15)
C570.035 (2)0.0315 (17)0.041 (2)0.0039 (15)0.0073 (16)0.0028 (14)
C390.045 (2)0.0327 (17)0.0311 (17)0.0061 (15)0.0009 (15)0.0005 (14)
C310.0281 (18)0.0297 (15)0.0270 (16)0.0018 (13)0.0033 (13)0.0018 (12)
C80.0283 (18)0.0422 (18)0.0269 (16)0.0073 (14)0.0021 (13)0.0046 (13)
C40.046 (2)0.0362 (18)0.0314 (18)0.0051 (16)0.0009 (16)0.0069 (14)
C340.043 (2)0.0328 (16)0.0275 (16)0.0044 (15)0.0001 (15)0.0009 (13)
C50.038 (2)0.0404 (18)0.0295 (17)0.0089 (15)0.0084 (15)0.0010 (14)
C380.047 (2)0.0311 (16)0.0264 (16)0.0013 (15)0.0032 (15)0.0021 (13)
C130.065 (3)0.0323 (17)0.036 (2)0.0061 (18)0.0023 (19)0.0037 (15)
C20.0294 (18)0.0313 (15)0.0276 (16)0.0034 (13)0.0006 (14)0.0029 (13)
C250.0261 (18)0.0308 (16)0.051 (2)0.0015 (14)0.0002 (17)0.0022 (14)
C510.0250 (18)0.048 (2)0.041 (2)0.0015 (15)0.0041 (16)0.0017 (16)
C560.033 (2)0.0351 (17)0.050 (2)0.0008 (15)0.0056 (17)0.0034 (15)
C320.0249 (17)0.0408 (17)0.0324 (17)0.0003 (14)0.0015 (14)0.0001 (14)
C230.036 (2)0.0326 (16)0.0355 (18)0.0058 (14)0.0015 (15)0.0003 (14)
C490.039 (2)0.0307 (17)0.0396 (19)0.0105 (15)0.0014 (15)0.0005 (14)
C350.0341 (19)0.0342 (16)0.0286 (17)0.0003 (14)0.0033 (14)0.0031 (13)
C120.068 (3)0.040 (2)0.035 (2)0.0235 (19)0.004 (2)0.0051 (16)
C110.050 (2)0.049 (2)0.0305 (18)0.0188 (17)0.0003 (16)0.0023 (16)
C420.117 (5)0.0329 (19)0.045 (2)0.002 (2)0.008 (3)0.0007 (18)
C430.100 (4)0.039 (2)0.053 (3)0.019 (2)0.015 (3)0.0016 (19)
C440.064 (3)0.047 (2)0.046 (2)0.009 (2)0.008 (2)0.0054 (18)
C410.074 (3)0.0338 (18)0.037 (2)0.0100 (19)0.005 (2)0.0015 (15)
C530.052 (3)0.060 (2)0.043 (2)0.013 (2)0.0028 (19)0.0103 (19)
Geometric parameters (Å, º) top
S7—C61.763 (4)O52—C531.416 (5)
S7—C81.775 (4)C15—H15A0.9900
S37—C381.761 (4)C15—H15B0.9900
S37—C361.769 (4)C1—C61.388 (5)
O3—C271.258 (4)C1—C21.398 (5)
O4—C271.276 (4)C9—C81.401 (5)
O5—C541.252 (4)C24—C251.499 (5)
O1—C241.221 (4)C54—C551.504 (5)
O2—C241.309 (5)C33—C341.380 (5)
O2—H2O0.8400C33—C321.393 (5)
O22—C31.369 (4)C19—H19A0.9800
O22—C231.429 (4)C19—H19B0.9800
O7—C571.227 (4)C19—H19C0.9800
O6—C541.277 (4)C3—C41.389 (5)
N48—C501.491 (4)C3—C21.397 (5)
N48—C491.494 (4)C26—C251.343 (5)
N48—C471.504 (4)C26—H260.9500
N48—H48N1.0000C6—C51.409 (5)
N18—C201.487 (4)C55—C561.346 (5)
N18—C191.496 (4)C55—H550.9500
N18—C171.504 (4)C57—C561.490 (5)
N18—H18N1.0000C39—C381.401 (5)
O8—C571.293 (5)C39—C441.402 (5)
O8—H8O0.8400C31—C321.393 (5)
N10—C11.425 (4)C8—C111.382 (5)
N10—C91.426 (4)C4—C51.372 (5)
N10—C151.463 (4)C4—H40.9500
C16—C211.520 (5)C34—C351.392 (5)
C16—C171.527 (4)C34—H340.9500
C16—C151.544 (4)C5—H50.9500
C16—H161.0000C38—C411.383 (5)
C20—H20A0.9800C13—C121.383 (6)
C20—H20B0.9800C13—H130.9500
C20—H20C0.9800C2—H20.9500
C27—C261.494 (5)C25—H250.9500
C17—H17A0.9900C51—H51A0.9800
C17—H17B0.9900C51—H51B0.9800
N40—C311.406 (4)C51—H51C0.9800
N40—C391.426 (4)C56—H560.9500
N40—C451.453 (4)C32—H320.9500
C36—C351.396 (5)C23—H23A0.9800
C36—C311.406 (5)C23—H23B0.9800
C46—C471.519 (4)C23—H23C0.9800
C46—C511.525 (5)C49—H49A0.9800
C46—C451.543 (5)C49—H49B0.9800
C46—H461.0000C49—H49C0.9800
C45—H45A0.9900C35—H350.9500
C45—H45B0.9900C12—C111.387 (6)
C47—H47A0.9900C12—H120.9500
C47—H47B0.9900C11—H110.9500
C50—H50A0.9800C42—C431.379 (8)
C50—H50B0.9800C42—C411.388 (7)
C50—H50C0.9800C42—H420.9500
C14—C91.391 (5)C43—C441.399 (6)
C14—C131.401 (5)C43—H430.9500
C14—H140.9500C44—H440.9500
C21—H21A0.9800C41—H410.9500
C21—H21B0.9800C53—H53A0.9800
C21—H21C0.9800C53—H53B0.9800
O52—C331.369 (4)C53—H53C0.9800
C6—S7—C897.88 (16)N18—C19—H19A109.5
C38—S37—C3697.47 (17)N18—C19—H19B109.5
C24—O2—H2O109.5H19A—C19—H19B109.5
C3—O22—C23117.5 (2)N18—C19—H19C109.5
C50—N48—C49109.7 (3)H19A—C19—H19C109.5
C50—N48—C47110.5 (3)H19B—C19—H19C109.5
C49—N48—C47112.8 (2)O22—C3—C4116.6 (3)
C50—N48—H48N107.9O22—C3—C2123.5 (3)
C49—N48—H48N107.9C4—C3—C2119.9 (3)
C47—N48—H48N107.9C25—C26—C27130.8 (3)
C20—N18—C19110.9 (3)C25—C26—H26114.6
C20—N18—C17109.6 (3)C27—C26—H26114.6
C19—N18—C17112.0 (2)C1—C6—C5119.5 (3)
C20—N18—H18N108.1C1—C6—S7119.1 (3)
C19—N18—H18N108.1C5—C6—S7121.2 (3)
C17—N18—H18N108.1C56—C55—C54130.1 (4)
C57—O8—H8O109.5C56—C55—H55114.9
C1—N10—C9117.4 (3)C54—C55—H55114.9
C1—N10—C15119.4 (3)O7—C57—O8122.2 (3)
C9—N10—C15118.0 (3)O7—C57—C56117.5 (4)
C21—C16—C17114.1 (3)O8—C57—C56120.2 (3)
C21—C16—C15111.4 (3)C38—C39—C44119.1 (3)
C17—C16—C15106.0 (2)C38—C39—N40119.1 (3)
C21—C16—H16108.4C44—C39—N40121.7 (4)
C17—C16—H16108.4C32—C31—N40121.7 (3)
C15—C16—H16108.4C32—C31—C36118.7 (3)
N18—C20—H20A109.5N40—C31—C36119.5 (3)
N18—C20—H20B109.5C11—C8—C9120.9 (3)
H20A—C20—H20B109.5C11—C8—S7120.6 (3)
N18—C20—H20C109.5C9—C8—S7118.5 (3)
H20A—C20—H20C109.5C5—C4—C3120.0 (3)
H20B—C20—H20C109.5C5—C4—H4120.0
O3—C27—O4123.0 (3)C3—C4—H4120.0
O3—C27—C26116.2 (3)C33—C34—C35119.1 (3)
O4—C27—C26120.8 (3)C33—C34—H34120.5
N18—C17—C16114.6 (3)C35—C34—H34120.5
N18—C17—H17A108.6C4—C5—C6120.7 (3)
C16—C17—H17A108.6C4—C5—H5119.7
N18—C17—H17B108.6C6—C5—H5119.7
C16—C17—H17B108.6C41—C38—C39120.2 (4)
H17A—C17—H17B107.6C41—C38—S37121.3 (3)
C31—N40—C39117.2 (3)C39—C38—S37118.5 (2)
C31—N40—C45121.6 (3)C12—C13—C14120.7 (4)
C39—N40—C45118.9 (3)C12—C13—H13119.7
C35—C36—C31120.1 (3)C14—C13—H13119.7
C35—C36—S37121.7 (3)C3—C2—C1120.2 (3)
C31—C36—S37118.1 (2)C3—C2—H2119.9
C47—C46—C51112.9 (3)C1—C2—H2119.9
C47—C46—C45108.6 (3)C26—C25—C24130.5 (3)
C51—C46—C45110.1 (3)C26—C25—H25114.8
C47—C46—H46108.4C24—C25—H25114.8
C51—C46—H46108.4C46—C51—H51A109.5
C45—C46—H46108.4C46—C51—H51B109.5
N40—C45—C46110.0 (3)H51A—C51—H51B109.5
N40—C45—H45A109.7C46—C51—H51C109.5
C46—C45—H45A109.7H51A—C51—H51C109.5
N40—C45—H45B109.7H51B—C51—H51C109.5
C46—C45—H45B109.7C55—C56—C57130.5 (4)
H45A—C45—H45B108.2C55—C56—H56114.7
N48—C47—C46113.8 (3)C57—C56—H56114.7
N48—C47—H47A108.8C33—C32—C31120.4 (3)
C46—C47—H47A108.8C33—C32—H32119.8
N48—C47—H47B108.8C31—C32—H32119.8
C46—C47—H47B108.8O22—C23—H23A109.5
H47A—C47—H47B107.7O22—C23—H23B109.5
N48—C50—H50A109.5H23A—C23—H23B109.5
N48—C50—H50B109.5O22—C23—H23C109.5
H50A—C50—H50B109.5H23A—C23—H23C109.5
N48—C50—H50C109.5H23B—C23—H23C109.5
H50A—C50—H50C109.5N48—C49—H49A109.5
H50B—C50—H50C109.5N48—C49—H49B109.5
C9—C14—C13119.6 (3)H49A—C49—H49B109.5
C9—C14—H14120.2N48—C49—H49C109.5
C13—C14—H14120.2H49A—C49—H49C109.5
C16—C21—H21A109.5H49B—C49—H49C109.5
C16—C21—H21B109.5C34—C35—C36120.6 (3)
H21A—C21—H21B109.5C34—C35—H35119.7
C16—C21—H21C109.5C36—C35—H35119.7
H21A—C21—H21C109.5C13—C12—C11119.7 (3)
H21B—C21—H21C109.5C13—C12—H12120.1
C33—O52—C53114.9 (3)C11—C12—H12120.1
N10—C15—C16111.9 (3)C8—C11—C12120.0 (4)
N10—C15—H15A109.2C8—C11—H11120.0
C16—C15—H15A109.2C12—C11—H11120.0
N10—C15—H15B109.2C43—C42—C41119.6 (4)
C16—C15—H15B109.2C43—C42—H42120.2
H15A—C15—H15B107.9C41—C42—H42120.2
C6—C1—C2119.6 (3)C42—C43—C44120.7 (4)
C6—C1—N10118.6 (3)C42—C43—H43119.7
C2—C1—N10121.9 (3)C44—C43—H43119.7
C14—C9—C8119.1 (3)C43—C44—C39119.6 (4)
C14—C9—N10122.3 (3)C43—C44—H44120.2
C8—C9—N10118.6 (3)C39—C44—H44120.2
O1—C24—O2121.8 (3)C38—C41—C42120.7 (4)
O1—C24—C25118.3 (3)C38—C41—H41119.7
O2—C24—C25119.9 (3)C42—C41—H41119.7
O5—C54—O6123.5 (3)O52—C53—H53A109.5
O5—C54—C55115.8 (3)O52—C53—H53B109.5
O6—C54—C55120.6 (3)H53A—C53—H53B109.5
O52—C33—C34124.6 (3)O52—C53—H53C109.5
O52—C33—C32114.3 (3)H53A—C53—H53C109.5
C34—C33—C32121.1 (3)H53B—C53—H53C109.5
Hydrogen-bond geometry (Å, º) top
Cg is the centroid of the C31–C36 ring.
D—H···AD—HH···AD···AD—H···A
O2—H2O···O40.841.612.452 (3)178
O8—H8O···O60.841.612.443 (4)174
N18—H18N···O3i1.001.732.716 (3)170
N48—H48N···O5ii1.001.742.710 (3)164
N48—H48N···O6ii1.002.633.332 (4)128
C11—H11···O3iii0.952.523.316 (5)141
C14—H14···O10.952.533.466 (5)167
C17—H17A···O10.992.433.340 (4)153
C19—H19B···O7iii0.992.493.449 (5)166
C23—H23A···O52iv0.982.563.518 (5)167
C23—H23C···Cg0.982.473.421 (4)145
C47—H47A···O7v0.992.343.296 (4)161
C49—H49B···O10.982.393.333 (5)163
C50—H50B···O3vi0.982.553.278 (4)131
C53—H53C···O4vii0.982.563.479 (5)156
Symmetry codes: (i) x+1, y1/2, 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) x1/2, y+3/2, z+1; (vi) x, y1/2, z+3/2; (vii) x+1/2, y+1, z1/2.
Hydrogen-bond geometry (Å, º) top
Cg is the centroid of the C31–C36 ring.
D—H···AD—HH···AD···AD—H···A
O2—H2O···O40.841.612.452 (3)178
O8—H8O···O60.841.612.443 (4)174
N18—H18N···O3i1.001.732.716 (3)170
N48—H48N···O5ii1.001.742.710 (3)164
N48—H48N···O6ii1.002.633.332 (4)128
C11—H11···O3iii0.952.523.316 (5)141
C14—H14···O10.952.533.466 (5)167
C17—H17A···O10.992.433.340 (4)153
C19—H19B···O7iii0.992.493.449 (5)166
C23—H23A···O52iv0.982.563.518 (5)167
C23—H23C···Cg0.982.473.421 (4)145
C47—H47A···O7v0.992.343.296 (4)161
C49—H49B···O10.982.393.333 (5)163
C50—H50B···O3vi0.982.553.278 (4)131
C53—H53C···O4vii0.982.563.479 (5)156
Symmetry codes: (i) x+1, y1/2, 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) x1/2, y+3/2, z+1; (vi) x, y1/2, z+3/2; (vii) x+1/2, y+1, z1/2.

Experimental details

Crystal data
Chemical formulaC19H25N2OS+·C4H3O4
Mr444.53
Crystal system, space groupOrthorhombic, P212121
Temperature (K)103
a, b, c (Å)11.6395 (5), 19.0487 (6), 20.4977 (7)
V3)4544.7 (3)
Z8
Radiation typeMo Kα
µ (mm1)0.18
Crystal size (mm)0.5 × 0.3 × 0.2
Data collection
DiffractometerR-AXIS RAPID
Absorption correctionNumerical
NUMABS; Higashi, 2002
Tmin, Tmax0.893, 0.971
No. of measured, independent and
observed [I > 2σ(I)] reflections
105320, 10363, 8459
Rint0.085
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.133, 1.05
No. of reflections10363
No. of parameters569
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.67, 0.31
Absolute structureFlack x determined using 3169 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013
Absolute structure parameter0.02 (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.

References

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Volume 72| Part 5| May 2016| Pages 612-615
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