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The dimethyl sulfoxide hemisolvate of perindoprilat [sys­tem­atic name: (1S)-2-((S)-{1-[(2S,3aS,7aS)-2-carb­oxy­octahydro-1H-indol-1-yl]-1-oxopropan-2-yl}aza­nium­yl)pentanoate di­methyl sulfoxide hemisolvate], C17H28N2O5·0.5C2H6OS, an active metabolite of perindopril, has been synthesized, structurally characterized by single-crystal X-ray diffraction and compared with its ethanol disolvate analogue [Pascard et al. (1991). J. Med. Chem. 34, 663–669]. Both compounds crystallize in the ortho­rhom­bic P212121 space group in the same zwitterionic form, with a protonated alanine N atom and an anionic carboxylate group at the n-alkyl chain. The three structural units present in the unit cell (two zwitterions and the solvent mol­ecule) are held together by a rich system of O—H...O, N—H...O and C—H...O hydrogen-bond con­tacts.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112032349/fg3257sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112032349/fg3257Isup2.hkl
Contains datablock I

CCDC reference: 908131

Comment top

Perindopril, a perhydroindole derivative (systematic name: (2S,3aS,7aS)-1-{(2S)-2-{[(2S)-1-ethoxy-1-oxopentan-2-yl]amino}propanoyl}-2,3,3a,4,5,6,7,7a-octahydroindole-2-carboxylic acid), is a powerful angiotensin-converting enzyme (ACE) inhibitor, a zinc metalloenzyme involved in the control of blood pressure (Opie, 1994). Furthermore, this prodrug possesses vasculoprotective or antithrombotic properties, important in terms of cardiovascular morbidity (Remková et al., 2008, Remková & Remko 2010). Perindopril is metabolized in vivo to its biologically active diacid form, namely perindoprilat, by hepatic esterase through the hydrolysis of ester groups (Kelly & O'Malley, 1990). The prodrug also undergoes glucuronidation and further hydrolysis to biologically inactive perindoprilat glucuronide (Grislain et al., 1990). Apart from that, a few other metabolites are formed, such as dehydrated perindopril and the diastereoisomers of dehydrated perindoprilat, which are also inactive (Medenica et al., 2007). Commercially used pharmaceutically effective forms of perindopril are its tert-butylamine and L-arginine salts. Only the enantiomer having all five asymmetric C atoms in the S configuration is used as an antihypertensive agent. Its R enantiomer is a byproduct in the synthesis of perindopril (Vincent & Schiavi, 1991). Although perindopril was first synthesized in 1982 (Vincent et al., 1982), its three-dimensional structure was unknown until 2011, when we presented the first crystal structures of the tert-butylamine salts [see Cambridge Structural Database (CSD, Version 5.31; Allen, 2002) refcodes IVEGIA and IVEGOG (Remko et al., 2011)] as part of our studies of perindoprilat polymorphism. Up to now, only one crystal structure of perindoprilat has been reported (Pascard et al., 1991; CSD refcode SIWBUV) in the form of its ethanol disolvate, (II).

This work concerns the crystal structure of perindoprilat dimethyl sulfoxide hemisolvate, (I), studied at 100 K and refined to an R factor of 0.027. The asymmetric unit of (I) contains two perindoprilat zwitterionic molecules (A and B) and one dimethyl sulfoxide solvent molecule (Fig. 1). Both perindoprilat molecules have an S configuration at all five chiral C atoms. The Flack parameter of 0.028 (11) (Flack, 1983) confirms this assignment. Two H atoms at each alanine N2 atom were unquestionably located in the electron-density map, which together with the equalized C—O bond lengths in the carboxyl groups confirms the presence of the zwitterionic form of perindoprilat in the studied crystal (Fig. 1).

The conformations of the two crystallographically independent zwitterions of (I) and of the ethanol disolvate, (II) (Pascard et al., 1991), are similar due to several features present in the structures, i.e. the rigid bicyclic system, an O3···N2 intermolecular hydrogen bond, several planar amide fragments and many groups involved in hydrogen bonds (Table 1 and Fig. 2). The six-membered rings of both molecules of (I) possess the same slightly deformed chair conformation, as indicated by the Cremer–Pople puckering parameters (Cremer & Pople, 1975), having a total puckering amplitude Q of 0.5524 (15) and 0.5387 (15) Å and with θ = 164.60 (16) and 166.69 (16)° for molecules A and B, respectively. The proline rings are in an envelope conformation, with a puckering amplitude Q of 0.3776 (14) and ϕ = 285.5 (2) for molecule A, and with Q = 0.3928 (15) Å and ϕ = 287.8 (2)° for molecule B. The amide systems are planar and the C15-terminal carboxyl groups are axial. The dihedral angles between the alanine methyl group and the amide plane (O1/C9/C10/C16) are nearly identical in both molecules [67.80 (16)° in A and 68.75 (15)° in B]. On the other hand, the conformations of the terminal alkyl chain, being the most obviously flexible part of (I), are quite different for molecules A and B (Fig. 3). They adopt either a synclinal or an antiperiplanar conformation, with N2—C11—C12—C13 torsion angles of 73.78 (15) and -179.38 (12)° for molecules A and B, respectively.

Another point of interest is the packing motifs of (I), which are dominated by intermolecular O—H···O and N—H···O hydrogen bonds (Table 1 and Fig. 2). The analysis of these hydrogen bonds shows that molecules A and B generate separate infinite 11-membered chains, with a graph-set motif of C(11) [according to the graph-set definition of Etter et al. (1990) and Bernstein et al. (1995)], through O5A—H5OA···O2A(x + 1/2, -y + 1/2, -z) and O5B—H5OB···O2B(x - 1/2, -y + 1/2, -z + 1) interactions that run in the [100] direction. Dimethyl sulfoxide molecules bridge the perindoprilat molecules via N2A—H2NA···O1S and N2B—H2ND···O1S hydrogen bonds. As a result, nine-membered rings with the graph-set motif R32(9) are generated (Fig. 2). The crystal packing is also stabilized by the formation of hydrogen-bonded layers, which contain R66(38) rings formed via O5A—H5OAv···O2A, O5B–H5OB···O2Bii, N2B—H2NCii···O3Aiii, N2A—H2NBiv···O3Bvi and N2B—H2NCvi···O3A hydrogen bonds (symmetry codes as in Fig. 2). In addition to the hydrogen bonds listed in Table 1, geometry calculations show several weak C—H···O separations, with H···O distances in the range 2.29–2.58 Å and C—H···O angles in the range 129–168°.

Related literature top

For related literature, see: Allen (2002); Bernstein et al. (1995); Cremer & Pople (1975); Etter et al. (1990); Flack (1983); Grislain et al. (1990); Kelly & O'Malley (1990); Medenica et al. (2007); Opie (1994); Pascard et al. (1991); Remko et al. (2011); Remková & Remko (2010); Remková et al. (2008); Vincent & Schiavi (1991); Vincent et al. (1982).

Experimental top

Perindoprilat was synthesized according to the method of Vincent et al. (1982). Crystals of (I) suitable for single-crystal X-ray structure analysis were obtained via controlled evaporation of a dimethyl sulfoxide–ethanol (Solvent ratio?) solution at room temperature.

Refinement top

H atoms were located in difference Fourier maps. C-bound H atoms were subsequently geometrically optimized and allowed for as riding atoms, with C—H = 0.98 Å for aromatic, 0.99 Å for methylene and 1.00 Å for methyl groups, and with Uiso(H) = 1.2Ueq(C) [Added text OK?]. H atoms bonded to N and O atoms were refined freely.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Dashed lines indicate hydrgen bonds. [Added text OK?]
[Figure 2] Fig. 2. The intermolecular O—H···O and N—H···O hydrogen bonds of (I) (dashed lines) determining the packing of molecules in the crystal structure. Only H atoms participating in hydrogen bonds are shown. [Symmetry codes: (iii) x-1/2, -y+1/2, -z+1; (iv) -x+1, y+1/2, -z+1/2; (v) x-1/2, -y+1/2, -z; (vi) -x+1/2, -y+1, z+1/2; (vii) -x+1/2, -y+1, z-1/2.]
[Figure 3] Fig. 3. A superimposition of molecule A of (I) (light grey; turquoise in the electronic version of the paper), molecule B of (I) (dark grey; dark blue in the electronic version of the paper) and (II) (medium grey; dark grey in the electronic version of the paper) on their common amide plane. H atoms have been omitted for clarity.
(1S)-2-((S)-{1-[(2S,3aS,7aS)-2- carboxyoctahydro-1H-indol-1-yl]-1-oxopropan-2-yl}azaniumyl)pentanoate dimethyl sulfoxide hemisolvate top
Crystal data top
C17H28N2O5·0.5C2H6OSF(000) = 1640
Mr = 379.49Dx = 1.236 Mg m3
Orthorhombic, P212121Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2abCell parameters from 9715 reflections
a = 10.3504 (7) Åθ = 4.5–71.4°
b = 16.0908 (11) ŵ = 1.21 mm1
c = 24.4828 (16) ÅT = 100 K
V = 4077.5 (5) Å3Plate, colourless
Z = 80.40 × 0.30 × 0.15 mm
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer
7427 independent reflections
Radiation source: 30W microsource with MonoCap capillary7382 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
Detector resolution: 18.4 pixels mm-1θmax = 68.0°, θmin = 3.3°
ω scansh = 1212
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1919
Tmin = 0.680, Tmax = 0.835l = 2929
71530 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.070 w = 1/[σ2(Fo2) + (0.0421P)2 + 0.9247P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
7427 reflectionsΔρmax = 0.29 e Å3
499 parametersΔρmin = 0.20 e Å3
0 restraintsAbsolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.028 (11)
Crystal data top
C17H28N2O5·0.5C2H6OSV = 4077.5 (5) Å3
Mr = 379.49Z = 8
Orthorhombic, P212121Cu Kα radiation
a = 10.3504 (7) ŵ = 1.21 mm1
b = 16.0908 (11) ÅT = 100 K
c = 24.4828 (16) Å0.40 × 0.30 × 0.15 mm
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer
7427 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
7382 reflections with I > 2σ(I)
Tmin = 0.680, Tmax = 0.835Rint = 0.030
71530 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.027H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.070Δρmax = 0.29 e Å3
S = 1.04Δρmin = 0.20 e Å3
7427 reflectionsAbsolute structure: Flack (1983), with how many Friedel pairs?
499 parametersAbsolute structure parameter: 0.028 (11)
0 restraints
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1A1.03014 (11)0.18251 (6)0.08716 (4)0.0291 (3)
O2A0.80045 (10)0.46198 (6)0.11033 (4)0.0255 (3)
O3A0.96995 (10)0.46208 (6)0.16696 (4)0.0218 (3)
O4A1.28173 (10)0.17863 (6)0.00249 (4)0.0270 (3)
O5A1.13075 (10)0.12794 (6)0.05920 (4)0.0231 (3)
N1A1.09829 (11)0.29425 (7)0.03878 (4)0.0186 (3)
N2A0.98014 (11)0.29298 (7)0.17363 (4)0.0183 (3)
C1A1.07950 (13)0.25090 (8)0.01339 (5)0.0194 (3)
C2A1.10385 (14)0.31879 (8)0.05670 (5)0.0226 (4)
C3A1.07694 (13)0.39985 (8)0.02629 (6)0.0206 (4)
C4A1.13110 (13)0.47780 (8)0.05383 (6)0.0227 (4)
C5A1.27712 (13)0.48653 (8)0.04729 (6)0.0228 (4)
C6A1.31235 (13)0.48381 (9)0.01324 (6)0.0242 (4)
C7A1.27535 (13)0.39921 (8)0.03662 (5)0.0219 (4)
C8A1.13025 (13)0.38344 (8)0.03115 (5)0.0185 (3)
C9A1.07198 (13)0.25420 (8)0.08533 (6)0.0219 (4)
C10A1.09941 (13)0.29981 (8)0.13888 (5)0.0211 (4)
C11A0.86286 (13)0.33255 (8)0.14805 (5)0.0195 (4)
C12A0.74049 (14)0.31176 (9)0.18026 (6)0.0250 (4)
C13A0.72543 (15)0.35684 (10)0.23466 (6)0.0303 (4)
C14A0.59370 (18)0.33723 (14)0.26007 (8)0.0476 (6)
C15A1.17555 (13)0.18115 (8)0.02238 (5)0.0192 (4)
C16A1.21299 (15)0.25891 (10)0.16777 (6)0.0319 (4)
C17A0.88036 (13)0.42726 (8)0.14086 (5)0.0184 (3)
O1B0.96570 (10)0.12118 (6)0.44781 (4)0.0246 (3)
O2B1.18563 (11)0.32385 (6)0.33960 (4)0.0301 (3)
O3B1.03004 (10)0.28479 (6)0.28259 (4)0.0228 (3)
O4B0.71588 (9)0.19251 (7)0.52240 (4)0.0275 (3)
O5B0.86247 (10)0.20701 (7)0.58912 (4)0.0274 (3)
N1B0.89488 (11)0.25451 (7)0.44605 (4)0.0181 (3)
N2B0.99902 (11)0.13592 (7)0.33210 (5)0.0185 (3)
C1B0.91490 (13)0.26547 (8)0.50490 (5)0.0193 (4)
C2B0.89045 (14)0.35889 (8)0.51447 (6)0.0241 (4)
C3B0.91514 (13)0.39754 (8)0.45841 (6)0.0217 (4)
C4B0.86326 (14)0.48565 (8)0.45019 (6)0.0267 (4)
C5B0.71757 (15)0.48979 (9)0.44062 (7)0.0303 (4)
C6B0.67570 (14)0.42949 (9)0.39591 (6)0.0279 (4)
C7B0.71221 (13)0.34078 (8)0.41173 (6)0.0236 (4)
C8B0.85830 (12)0.33317 (8)0.41901 (5)0.0186 (3)
C9B0.92176 (12)0.18083 (8)0.42288 (5)0.0188 (3)
C10B0.88685 (13)0.17203 (8)0.36248 (5)0.0197 (3)
C11B1.12511 (14)0.18023 (8)0.33804 (5)0.0210 (3)
C12B1.22102 (14)0.13182 (9)0.30184 (6)0.0266 (4)
C13B1.35855 (15)0.16495 (10)0.30157 (7)0.0342 (5)
C14B1.44372 (17)0.11066 (13)0.26491 (9)0.0494 (6)
C15B0.81958 (13)0.21552 (8)0.53841 (5)0.0201 (3)
C16B0.76990 (15)0.11493 (9)0.35671 (6)0.0275 (4)
C17B1.11211 (13)0.27146 (7)0.31868 (5)0.0190 (3)
S1S0.88079 (4)0.05813 (2)0.18727 (1)0.0316 (1)
O1S0.90813 (11)0.13526 (6)0.22131 (4)0.0278 (3)
C1S1.01876 (17)0.00629 (10)0.19497 (7)0.0375 (5)
C2S0.77414 (18)0.00566 (12)0.22695 (10)0.0524 (7)
H2NA0.9647 (18)0.2390 (12)0.1817 (7)0.034 (5)*
H1A0.989100.229500.016300.0230*
H2NB0.9961 (16)0.3175 (11)0.2059 (7)0.023 (4)*
H2A1.044700.312200.088200.0270*
H2B1.194200.316900.070000.0270*
H5OA1.199 (2)0.0949 (14)0.0707 (8)0.048 (6)*
H3A0.981100.406500.023300.0250*
H4A1.109800.476100.093200.0270*
H4B1.088600.527400.038000.0270*
H5A1.321300.440800.066800.0270*
H5B1.306100.539800.063300.0270*
H6A1.406300.493100.017800.0290*
H6B1.265800.528300.033100.0290*
H7A1.323400.355100.017100.0260*
H7B1.300100.396800.075700.0260*
H8A1.082100.417800.058500.0220*
H10A1.119200.359600.131400.0250*
H11A0.852700.308000.110800.0230*
H12A0.664700.324900.157200.0300*
H12B0.739300.251200.187300.0300*
H13A0.733300.417500.228800.0360*
H13B0.795000.339300.259900.0360*
H14A0.525000.354100.234900.0710*
H14B0.584500.367600.294500.0710*
H14C0.587300.277400.267100.0710*
H16A1.227000.285900.203200.0480*
H16B1.290800.264600.145300.0480*
H16C1.194300.199800.173500.0480*
H1B1.005600.250600.515100.0230*
H2C0.800600.369000.526600.0290*
H2D0.950700.381500.542100.0290*
H3B1.010700.399100.452500.0260*
H2NC1.0070 (18)0.0844 (12)0.3401 (7)0.029 (4)*
H4C0.907800.511000.418500.0320*
H4D0.884700.519200.482800.0320*
H2ND0.9786 (17)0.1364 (11)0.2969 (8)0.023 (4)*
H5C0.693300.547100.430000.0360*
H5D0.671800.476100.475000.0360*
H5OB0.803 (2)0.1953 (14)0.6081 (9)0.051 (6)*
H6C0.581100.433300.390600.0330*
H6D0.718300.444500.361100.0330*
H7C0.683000.301900.382900.0280*
H7D0.668300.325500.446200.0280*
H8B0.902100.337400.382700.0220*
H10B0.865600.228000.347100.0240*
H11B1.154100.178600.377000.0250*
H12C1.222900.073300.314300.0320*
H12D1.188100.132100.263900.0320*
H13C1.393300.165000.339200.0410*
H13D1.359000.222900.287900.0410*
H14D1.441500.053100.278000.0740*
H14E1.532800.131300.266000.0740*
H14F1.411400.112900.227300.0740*
H16D0.744100.112100.318200.0410*
H16E0.698200.136900.378500.0410*
H16F0.792300.059100.369700.0410*
H1S11.093700.020700.178200.0560*
H1S21.003100.059800.177100.0560*
H1S31.035600.015300.233900.0560*
H2S10.811400.014600.263300.0790*
H2S20.762500.059300.208700.0790*
H2S30.690300.022100.230500.0790*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0417 (6)0.0174 (5)0.0281 (5)0.0044 (4)0.0080 (5)0.0004 (4)
O2A0.0336 (5)0.0176 (5)0.0254 (5)0.0003 (4)0.0075 (4)0.0010 (4)
O3A0.0256 (5)0.0168 (4)0.0230 (5)0.0020 (4)0.0007 (4)0.0012 (4)
O4A0.0235 (5)0.0234 (5)0.0340 (5)0.0034 (4)0.0013 (4)0.0025 (4)
O5A0.0283 (5)0.0188 (4)0.0221 (5)0.0003 (4)0.0041 (4)0.0027 (4)
N1A0.0205 (5)0.0150 (5)0.0202 (5)0.0002 (4)0.0019 (4)0.0013 (4)
N2A0.0240 (6)0.0139 (5)0.0169 (5)0.0002 (4)0.0003 (4)0.0015 (4)
C1A0.0193 (6)0.0192 (6)0.0197 (6)0.0026 (5)0.0001 (5)0.0001 (5)
C2A0.0284 (7)0.0189 (6)0.0205 (6)0.0007 (5)0.0037 (5)0.0015 (5)
C3A0.0174 (6)0.0188 (7)0.0255 (7)0.0010 (5)0.0004 (5)0.0017 (5)
C4A0.0251 (7)0.0175 (6)0.0254 (7)0.0027 (5)0.0005 (6)0.0030 (5)
C5A0.0262 (7)0.0196 (6)0.0225 (7)0.0020 (5)0.0049 (5)0.0015 (5)
C6A0.0232 (7)0.0247 (7)0.0247 (7)0.0068 (6)0.0021 (5)0.0013 (6)
C7A0.0212 (6)0.0230 (7)0.0215 (6)0.0013 (5)0.0021 (5)0.0016 (5)
C8A0.0199 (6)0.0141 (6)0.0215 (6)0.0008 (5)0.0034 (5)0.0002 (5)
C9A0.0222 (6)0.0183 (6)0.0252 (7)0.0027 (5)0.0037 (5)0.0007 (5)
C10A0.0239 (7)0.0195 (6)0.0199 (6)0.0000 (5)0.0028 (5)0.0022 (5)
C11A0.0237 (7)0.0162 (6)0.0187 (6)0.0003 (5)0.0022 (5)0.0009 (5)
C12A0.0259 (7)0.0221 (7)0.0270 (7)0.0021 (5)0.0002 (6)0.0033 (6)
C13A0.0283 (7)0.0365 (8)0.0261 (7)0.0035 (6)0.0006 (6)0.0000 (6)
C14A0.0368 (9)0.0666 (12)0.0395 (9)0.0113 (9)0.0120 (8)0.0100 (9)
C15A0.0233 (7)0.0158 (6)0.0185 (6)0.0039 (5)0.0049 (5)0.0036 (5)
C16A0.0271 (7)0.0371 (8)0.0316 (8)0.0055 (6)0.0003 (6)0.0031 (6)
C17A0.0234 (6)0.0161 (6)0.0158 (6)0.0002 (5)0.0031 (5)0.0012 (5)
O1B0.0325 (5)0.0200 (5)0.0213 (5)0.0053 (4)0.0020 (4)0.0024 (4)
O2B0.0406 (6)0.0184 (5)0.0314 (5)0.0030 (4)0.0150 (5)0.0034 (4)
O3B0.0306 (5)0.0187 (5)0.0192 (4)0.0007 (4)0.0051 (4)0.0028 (4)
O4B0.0216 (5)0.0293 (5)0.0317 (5)0.0034 (4)0.0011 (4)0.0042 (4)
O5B0.0285 (5)0.0344 (6)0.0194 (5)0.0043 (4)0.0043 (4)0.0017 (4)
N1B0.0196 (5)0.0181 (5)0.0167 (5)0.0001 (4)0.0016 (4)0.0005 (4)
N2B0.0280 (6)0.0124 (5)0.0150 (5)0.0031 (4)0.0024 (4)0.0016 (4)
C1B0.0183 (6)0.0222 (7)0.0175 (6)0.0002 (5)0.0003 (5)0.0025 (5)
C2B0.0284 (7)0.0213 (7)0.0227 (7)0.0036 (6)0.0009 (6)0.0047 (5)
C3B0.0192 (6)0.0196 (7)0.0264 (7)0.0020 (5)0.0030 (5)0.0021 (5)
C4B0.0312 (7)0.0178 (6)0.0310 (7)0.0002 (6)0.0029 (6)0.0036 (5)
C5B0.0300 (7)0.0228 (7)0.0381 (8)0.0078 (6)0.0047 (6)0.0039 (6)
C6B0.0215 (7)0.0254 (7)0.0367 (8)0.0059 (6)0.0003 (6)0.0002 (6)
C7B0.0207 (6)0.0215 (7)0.0286 (7)0.0002 (5)0.0003 (6)0.0010 (5)
C8B0.0201 (6)0.0156 (6)0.0200 (6)0.0005 (5)0.0035 (5)0.0004 (5)
C9B0.0183 (6)0.0183 (6)0.0197 (6)0.0009 (5)0.0036 (5)0.0010 (5)
C10B0.0239 (6)0.0159 (6)0.0194 (6)0.0028 (5)0.0018 (5)0.0011 (5)
C11B0.0226 (6)0.0194 (6)0.0210 (6)0.0015 (5)0.0015 (5)0.0038 (5)
C12B0.0292 (7)0.0211 (7)0.0295 (7)0.0023 (6)0.0017 (6)0.0019 (6)
C13B0.0253 (8)0.0350 (8)0.0422 (9)0.0019 (6)0.0015 (7)0.0048 (7)
C14B0.0291 (8)0.0518 (12)0.0674 (13)0.0071 (8)0.0099 (8)0.0146 (10)
C15B0.0197 (6)0.0182 (6)0.0225 (6)0.0026 (5)0.0037 (5)0.0014 (5)
C16B0.0293 (7)0.0284 (7)0.0248 (7)0.0036 (6)0.0005 (6)0.0039 (6)
C17B0.0257 (6)0.0152 (6)0.0162 (6)0.0024 (5)0.0032 (5)0.0009 (5)
S1S0.0490 (2)0.0204 (2)0.0254 (2)0.0019 (2)0.0118 (2)0.0054 (1)
O1S0.0446 (6)0.0162 (5)0.0227 (5)0.0009 (4)0.0051 (4)0.0009 (4)
C1S0.0400 (9)0.0282 (8)0.0442 (9)0.0023 (7)0.0102 (8)0.0111 (7)
C2S0.0387 (9)0.0338 (9)0.0847 (15)0.0119 (8)0.0198 (10)0.0296 (10)
Geometric parameters (Å, º) top
S1S—C2S1.793 (2)C11A—H11A1.0000
S1S—O1S1.5215 (10)C12A—H12B0.9900
S1S—C1S1.7746 (18)C12A—H12A0.9900
O1A—C9A1.2330 (16)C13A—H13A0.9900
O2A—C17A1.2470 (16)C13A—H13B0.9900
O3A—C17A1.2578 (16)C14A—H14B0.9800
O4A—C15A1.2027 (17)C14A—H14A0.9800
O5A—C15A1.3269 (16)C14A—H14C0.9800
O5A—H5OA0.93 (2)C16A—H16C0.9800
O1B—C9B1.2250 (16)C16A—H16B0.9800
O2B—C17B1.2458 (16)C16A—H16A0.9800
O3B—C17B1.2443 (16)C1B—C15B1.5141 (18)
O4B—C15B1.2012 (16)C1B—C2B1.5423 (18)
O5B—C15B1.3256 (16)C2B—C3B1.528 (2)
O5B—H5OB0.79 (2)C3B—C8B1.5328 (19)
N1A—C8A1.4846 (17)C3B—C4B1.5293 (18)
N1A—C1A1.4683 (16)C4B—C5B1.528 (2)
N1A—C9A1.3373 (18)C5B—C6B1.526 (2)
N2A—C11A1.5070 (17)C6B—C7B1.527 (2)
N2A—C10A1.5033 (17)C7B—C8B1.5275 (18)
N2A—H2NA0.905 (19)C9B—C10B1.5288 (17)
N2A—H2NB0.898 (17)C10B—C16B1.526 (2)
N1B—C1B1.4663 (16)C11B—C12B1.542 (2)
N1B—C9B1.3434 (17)C11B—C17B1.5485 (17)
N1B—C8B1.4777 (17)C12B—C13B1.520 (2)
N2B—C10B1.4963 (18)C13B—C14B1.532 (3)
N2B—C11B1.4942 (18)C1B—H1B1.0000
N2B—H2ND0.887 (19)C2B—H2C0.9900
N2B—H2NC0.856 (19)C2B—H2D0.9900
C1A—C2A1.5431 (18)C3B—H3B1.0000
C1A—C15A1.5154 (19)C4B—H4D0.9900
C2A—C3A1.5275 (19)C4B—H4C0.9900
C3A—C8A1.5336 (19)C5B—H5C0.9900
C3A—C4A1.5304 (19)C5B—H5D0.9900
C4A—C5A1.5263 (19)C6B—H6C0.9900
C5A—C6A1.527 (2)C6B—H6D0.9900
C6A—C7A1.5256 (19)C7B—H7D0.9900
C7A—C8A1.5290 (19)C7B—H7C0.9900
C9A—C10A1.5291 (19)C8B—H8B1.0000
C10A—C16A1.522 (2)C10B—H10B1.0000
C11A—C17A1.5448 (18)C11B—H11B1.0000
C11A—C12A1.529 (2)C12B—H12C0.9900
C12A—C13A1.525 (2)C12B—H12D0.9900
C13A—C14A1.532 (2)C13B—H13C0.9900
C1A—H1A1.0000C13B—H13D0.9900
C2A—H2B0.9900C14B—H14F0.9800
C2A—H2A0.9900C14B—H14D0.9800
C3A—H3A1.0000C14B—H14E0.9800
C4A—H4B0.9900C16B—H16D0.9800
C4A—H4A0.9900C16B—H16E0.9800
C5A—H5B0.9900C16B—H16F0.9800
C5A—H5A0.9900C1S—H1S10.9800
C6A—H6B0.9900C1S—H1S20.9800
C6A—H6A0.9900C1S—H1S30.9800
C7A—H7B0.9900C2S—H2S10.9800
C7A—H7A0.9900C2S—H2S20.9800
C8A—H8A1.0000C2S—H2S30.9800
C10A—H10A1.0000
C1S—S1S—C2S95.94 (8)H16A—C16A—H16C109.00
O1S—S1S—C1S105.58 (7)C10A—C16A—H16A109.00
O1S—S1S—C2S106.54 (8)C10A—C16A—H16B109.00
C15A—O5A—H5OA108.1 (13)H16A—C16A—H16B109.00
C15B—O5B—H5OB108.2 (16)C10A—C16A—H16C109.00
C1A—N1A—C8A112.29 (9)N1B—C1B—C2B104.08 (10)
C1A—N1A—C9A119.04 (11)N1B—C1B—C15B112.12 (11)
C8A—N1A—C9A128.20 (11)C2B—C1B—C15B109.16 (11)
C10A—N2A—C11A113.29 (9)C1B—C2B—C3B103.46 (11)
C10A—N2A—H2NA109.8 (12)C2B—C3B—C4B115.89 (12)
C11A—N2A—H2NA110.7 (12)C2B—C3B—C8B103.06 (10)
C11A—N2A—H2NB109.2 (11)C4B—C3B—C8B114.13 (11)
C10A—N2A—H2NB108.3 (11)C3B—C4B—C5B114.03 (11)
H2NA—N2A—H2NB105.2 (16)C4B—C5B—C6B111.27 (12)
C1B—N1B—C9B119.46 (11)C5B—C6B—C7B110.02 (12)
C8B—N1B—C9B128.30 (10)C6B—C7B—C8B110.46 (11)
C1B—N1B—C8B111.93 (10)N1B—C8B—C7B112.00 (10)
C10B—N2B—C11B116.36 (10)N1B—C8B—C3B101.45 (10)
C11B—N2B—H2NC110.8 (12)C3B—C8B—C7B113.53 (11)
C11B—N2B—H2ND107.4 (12)O1B—C9B—C10B119.81 (11)
C10B—N2B—H2ND107.1 (12)O1B—C9B—N1B123.92 (12)
C10B—N2B—H2NC109.7 (12)N1B—C9B—C10B116.18 (11)
H2NC—N2B—H2ND104.7 (16)N2B—C10B—C16B109.61 (11)
C2A—C1A—C15A108.50 (10)C9B—C10B—C16B109.44 (11)
N1A—C1A—C2A103.88 (10)N2B—C10B—C9B109.48 (10)
N1A—C1A—C15A113.04 (10)N2B—C11B—C17B110.28 (11)
C1A—C2A—C3A103.87 (10)C12B—C11B—C17B111.03 (11)
C2A—C3A—C4A114.73 (12)N2B—C11B—C12B105.39 (10)
C2A—C3A—C8A103.55 (10)C11B—C12B—C13B115.36 (12)
C4A—C3A—C8A114.41 (11)C12B—C13B—C14B109.97 (13)
C3A—C4A—C5A113.07 (11)O4B—C15B—C1B124.69 (12)
C4A—C5A—C6A109.61 (11)O5B—C15B—C1B110.13 (11)
C5A—C6A—C7A109.26 (11)O4B—C15B—O5B124.96 (12)
C6A—C7A—C8A111.21 (11)O3B—C17B—C11B116.11 (11)
N1A—C8A—C7A111.61 (11)O2B—C17B—O3B126.32 (11)
C3A—C8A—C7A113.90 (11)O2B—C17B—C11B117.55 (11)
N1A—C8A—C3A101.63 (10)C2B—C1B—H1B110.00
O1A—C9A—C10A118.89 (12)N1B—C1B—H1B110.00
O1A—C9A—N1A123.60 (13)C15B—C1B—H1B110.00
N1A—C9A—C10A117.49 (11)C3B—C2B—H2C111.00
C9A—C10A—C16A109.54 (11)C1B—C2B—H2D111.00
N2A—C10A—C16A109.86 (10)C1B—C2B—H2C111.00
N2A—C10A—C9A107.32 (10)C3B—C2B—H2D111.00
N2A—C11A—C17A111.70 (10)H2C—C2B—H2D109.00
C12A—C11A—C17A111.82 (11)C2B—C3B—H3B108.00
N2A—C11A—C12A111.13 (10)C4B—C3B—H3B108.00
C11A—C12A—C13A115.54 (12)C8B—C3B—H3B108.00
C12A—C13A—C14A110.36 (13)C3B—C4B—H4D109.00
O5A—C15A—C1A110.32 (11)H4C—C4B—H4D108.00
O4A—C15A—O5A124.93 (12)C5B—C4B—H4C109.00
O4A—C15A—C1A124.45 (12)C5B—C4B—H4D109.00
O2A—C17A—O3A126.44 (12)C3B—C4B—H4C109.00
O3A—C17A—C11A117.90 (11)C6B—C5B—H5D109.00
O2A—C17A—C11A115.63 (11)H5C—C5B—H5D108.00
C15A—C1A—H1A110.00C4B—C5B—H5C109.00
C2A—C1A—H1A110.00C4B—C5B—H5D109.00
N1A—C1A—H1A110.00C6B—C5B—H5C109.00
C1A—C2A—H2B111.00C5B—C6B—H6C110.00
C3A—C2A—H2A111.00C5B—C6B—H6D110.00
C3A—C2A—H2B111.00C7B—C6B—H6C110.00
H2A—C2A—H2B109.00C7B—C6B—H6D110.00
C1A—C2A—H2A111.00H6C—C6B—H6D108.00
C2A—C3A—H3A108.00C6B—C7B—H7D110.00
C8A—C3A—H3A108.00H7C—C7B—H7D108.00
C4A—C3A—H3A108.00C8B—C7B—H7C110.00
C5A—C4A—H4A109.00C8B—C7B—H7D110.00
H4A—C4A—H4B108.00C6B—C7B—H7C110.00
C3A—C4A—H4B109.00C7B—C8B—H8B110.00
C3A—C4A—H4A109.00C3B—C8B—H8B110.00
C5A—C4A—H4B109.00N1B—C8B—H8B110.00
H5A—C5A—H5B108.00C16B—C10B—H10B109.00
C6A—C5A—H5B110.00C9B—C10B—H10B109.00
C4A—C5A—H5A110.00N2B—C10B—H10B109.00
C4A—C5A—H5B110.00N2B—C11B—H11B110.00
C6A—C5A—H5A110.00C12B—C11B—H11B110.00
C5A—C6A—H6B110.00C17B—C11B—H11B110.00
C7A—C6A—H6A110.00C13B—C12B—H12D108.00
C5A—C6A—H6A110.00H12C—C12B—H12D107.00
H6A—C6A—H6B108.00C11B—C12B—H12D108.00
C7A—C6A—H6B110.00C13B—C12B—H12C108.00
C8A—C7A—H7A109.00C11B—C12B—H12C108.00
H7A—C7A—H7B108.00C12B—C13B—H13C110.00
C6A—C7A—H7B109.00C12B—C13B—H13D110.00
C6A—C7A—H7A109.00H13C—C13B—H13D108.00
C8A—C7A—H7B109.00C14B—C13B—H13C110.00
N1A—C8A—H8A110.00C14B—C13B—H13D110.00
C7A—C8A—H8A110.00C13B—C14B—H14E109.00
C3A—C8A—H8A110.00H14D—C14B—H14F109.00
N2A—C10A—H10A110.00C13B—C14B—H14F109.00
C9A—C10A—H10A110.00H14D—C14B—H14E109.00
C16A—C10A—H10A110.00C13B—C14B—H14D109.00
C17A—C11A—H11A107.00H14E—C14B—H14F110.00
N2A—C11A—H11A107.00C10B—C16B—H16F110.00
C12A—C11A—H11A107.00H16D—C16B—H16F109.00
C13A—C12A—H12B108.00H16E—C16B—H16F109.00
H12A—C12A—H12B107.00H16D—C16B—H16E110.00
C11A—C12A—H12B108.00C10B—C16B—H16D109.00
C13A—C12A—H12A108.00C10B—C16B—H16E109.00
C11A—C12A—H12A108.00S1S—C1S—H1S1110.00
C12A—C13A—H13B110.00S1S—C1S—H1S2109.00
C12A—C13A—H13A110.00S1S—C1S—H1S3109.00
C14A—C13A—H13B110.00H1S1—C1S—H1S2109.00
H13A—C13A—H13B108.00H1S1—C1S—H1S3109.00
C14A—C13A—H13A110.00H1S2—C1S—H1S3110.00
C13A—C14A—H14C110.00S1S—C2S—H2S1109.00
H14A—C14A—H14B109.00S1S—C2S—H2S2109.00
C13A—C14A—H14A109.00S1S—C2S—H2S3109.00
C13A—C14A—H14B109.00H2S1—C2S—H2S2109.00
H14B—C14A—H14C109.00H2S1—C2S—H2S3110.00
H14A—C14A—H14C109.00H2S2—C2S—H2S3109.00
H16B—C16A—H16C109.00
C8A—N1A—C1A—C2A0.85 (14)C3A—C4A—C5A—C6A55.15 (15)
C9A—N1A—C1A—C2A173.69 (12)C4A—C5A—C6A—C7A63.12 (14)
C8A—N1A—C1A—C15A118.25 (12)C5A—C6A—C7A—C8A60.44 (14)
C9A—N1A—C1A—C15A68.91 (15)C6A—C7A—C8A—N1A163.84 (10)
C9A—N1A—C8A—C7A88.24 (16)C6A—C7A—C8A—C3A49.46 (14)
C1A—N1A—C9A—O1A1.3 (2)N1A—C9A—C10A—N2A130.27 (12)
C8A—N1A—C9A—O1A170.23 (13)N1A—C9A—C10A—C16A110.51 (14)
C1A—N1A—C9A—C10A176.89 (11)O1A—C9A—C10A—N2A51.42 (16)
C1A—N1A—C8A—C3A22.03 (13)O1A—C9A—C10A—C16A67.80 (16)
C9A—N1A—C8A—C3A149.99 (13)N2A—C11A—C12A—C13A73.78 (15)
C1A—N1A—C8A—C7A99.73 (12)C17A—C11A—C12A—C13A51.79 (16)
C8A—N1A—C9A—C10A11.6 (2)N2A—C11A—C17A—O2A165.97 (11)
C11A—N2A—C10A—C9A61.32 (13)N2A—C11A—C17A—O3A15.88 (16)
C10A—N2A—C11A—C12A170.73 (10)C12A—C11A—C17A—O2A68.77 (15)
C10A—N2A—C11A—C17A63.63 (13)C12A—C11A—C17A—O3A109.37 (14)
C11A—N2A—C10A—C16A179.66 (11)C11A—C12A—C13A—C14A174.49 (13)
C9B—N1B—C1B—C2B173.21 (11)C2B—C1B—C15B—O4B91.23 (16)
C8B—N1B—C1B—C15B116.98 (12)C2B—C1B—C15B—O5B83.55 (13)
C9B—N1B—C1B—C15B68.94 (15)C15B—C1B—C2B—C3B143.16 (11)
C8B—N1B—C9B—O1B171.23 (12)N1B—C1B—C15B—O4B23.56 (18)
C1B—N1B—C9B—C10B174.67 (11)N1B—C1B—C2B—C3B23.28 (13)
C8B—N1B—C9B—C10B12.33 (19)N1B—C1B—C15B—O5B161.66 (11)
C1B—N1B—C8B—C3B24.39 (13)C1B—C2B—C3B—C8B38.26 (13)
C1B—N1B—C8B—C7B97.02 (13)C1B—C2B—C3B—C4B163.66 (11)
C9B—N1B—C8B—C7B89.55 (15)C4B—C3B—C8B—N1B164.47 (11)
C1B—N1B—C9B—O1B1.77 (19)C8B—C3B—C4B—C5B42.71 (17)
C8B—N1B—C1B—C2B0.87 (14)C2B—C3B—C8B—N1B37.95 (12)
C9B—N1B—C8B—C3B149.04 (13)C2B—C3B—C4B—C5B76.82 (16)
C11B—N2B—C10B—C16B174.36 (11)C4B—C3B—C8B—C7B44.14 (16)
C10B—N2B—C11B—C12B178.55 (11)C2B—C3B—C8B—C7B82.39 (13)
C10B—N2B—C11B—C17B58.64 (14)C3B—C4B—C5B—C6B50.34 (17)
C11B—N2B—C10B—C9B54.31 (14)C4B—C5B—C6B—C7B59.21 (16)
C15A—C1A—C2A—C3A144.21 (11)C5B—C6B—C7B—C8B60.49 (15)
N1A—C1A—C15A—O5A159.42 (11)C6B—C7B—C8B—N1B167.19 (11)
C2A—C1A—C15A—O4A88.05 (15)C6B—C7B—C8B—C3B53.02 (15)
N1A—C1A—C2A—C3A23.70 (13)O1B—C9B—C10B—C16B68.75 (15)
N1A—C1A—C15A—O4A26.61 (18)N1B—C9B—C10B—N2B132.01 (12)
C2A—C1A—C15A—O5A85.93 (13)N1B—C9B—C10B—C16B107.84 (13)
C1A—C2A—C3A—C8A37.43 (13)O1B—C9B—C10B—N2B51.40 (16)
C1A—C2A—C3A—C4A162.82 (11)N2B—C11B—C12B—C13B179.38 (12)
C2A—C3A—C4A—C5A75.11 (15)C17B—C11B—C12B—C13B61.22 (16)
C2A—C3A—C8A—C7A84.21 (13)N2B—C11B—C17B—O2B152.26 (12)
C4A—C3A—C8A—N1A161.54 (11)N2B—C11B—C17B—O3B29.14 (15)
C2A—C3A—C8A—N1A35.96 (12)C12B—C11B—C17B—O2B91.31 (14)
C4A—C3A—C8A—C7A41.38 (15)C12B—C11B—C17B—O3B87.30 (15)
C8A—C3A—C4A—C5A44.39 (16)C11B—C12B—C13B—C14B179.11 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2A—H2NA···O1S0.905 (19)2.017 (19)2.8912 (15)161.9 (16)
N2A—H2NB···O3B0.898 (17)1.981 (17)2.7204 (14)138.5 (15)
O5A—H5OA···O2Ai0.93 (2)1.70 (2)2.5972 (14)162.4 (19)
N2B—H2NC···O3Aii0.856 (19)1.990 (19)2.8157 (15)161.8 (16)
N2B—H2ND···O1S0.887 (19)1.989 (19)2.8710 (16)172.2 (17)
O5B—H5OB···O2Biii0.79 (2)1.79 (2)2.5773 (15)170 (2)
C1B—H1B···O4Biv1.002.533.2571 (17)129
C3A—H3A···O4Av1.002.563.3805 (17)140
C4B—H4D···O5Avi0.992.573.5169 (17)161
C1S—H1S3···O3Aii0.982.463.420 (2)168
C10A—H10A···O3A1.002.423.0143 (16)117
C10B—H10B···O3B1.002.503.0519 (16)115
C2S—H2S2···O2Bii0.982.293.218 (2)159
C12A—H12A···O5Av0.992.543.3191 (18)135
C12B—H12C···O2Aii0.992.583.4845 (18)151
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x+2, y1/2, z+1/2; (iii) x1/2, y+1/2, z+1; (iv) x+1/2, y+1/2, z+1; (v) x1/2, y+1/2, z; (vi) x+2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC17H28N2O5·0.5C2H6OS
Mr379.49
Crystal system, space groupOrthorhombic, P212121
Temperature (K)100
a, b, c (Å)10.3504 (7), 16.0908 (11), 24.4828 (16)
V3)4077.5 (5)
Z8
Radiation typeCu Kα
µ (mm1)1.21
Crystal size (mm)0.40 × 0.30 × 0.15
Data collection
DiffractometerBruker SMART APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.680, 0.835
No. of measured, independent and
observed [I > 2σ(I)] reflections
71530, 7427, 7382
Rint0.030
(sin θ/λ)max1)0.601
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.070, 1.04
No. of reflections7427
No. of parameters499
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.29, 0.20
Absolute structureFlack (1983), with how many Friedel pairs?
Absolute structure parameter0.028 (11)

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2A—H2NA···O1S0.905 (19)2.017 (19)2.8912 (15)161.9 (16)
N2A—H2NB···O3B0.898 (17)1.981 (17)2.7204 (14)138.5 (15)
O5A—H5OA···O2Ai0.93 (2)1.70 (2)2.5972 (14)162.4 (19)
N2B—H2NC···O3Aii0.856 (19)1.990 (19)2.8157 (15)161.8 (16)
N2B—H2ND···O1S0.887 (19)1.989 (19)2.8710 (16)172.2 (17)
O5B—H5OB···O2Biii0.79 (2)1.79 (2)2.5773 (15)170 (2)
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x+2, y1/2, z+1/2; (iii) x1/2, y+1/2, z+1.
 

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