Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112032349/fg3257sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112032349/fg3257Isup2.hkl |
CCDC reference: 908131
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.
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.
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).
C17H28N2O5·0.5C2H6OS | F(000) = 1640 |
Mr = 379.49 | Dx = 1.236 Mg m−3 |
Orthorhombic, P212121 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 9715 reflections |
a = 10.3504 (7) Å | θ = 4.5–71.4° |
b = 16.0908 (11) Å | µ = 1.21 mm−1 |
c = 24.4828 (16) Å | T = 100 K |
V = 4077.5 (5) Å3 | Plate, colourless |
Z = 8 | 0.40 × 0.30 × 0.15 mm |
Bruker SMART APEXII CCD area-detector diffractometer | 7427 independent reflections |
Radiation source: 30W microsource with MonoCap capillary | 7382 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 18.4 pixels mm-1 | θmax = 68.0°, θmin = 3.3° |
ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −19→19 |
Tmin = 0.680, Tmax = 0.835 | l = −29→29 |
71530 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.027 | H 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 reflections | Δρmax = 0.29 e Å−3 |
499 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.028 (11) |
C17H28N2O5·0.5C2H6OS | V = 4077.5 (5) Å3 |
Mr = 379.49 | Z = 8 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 10.3504 (7) Å | µ = 1.21 mm−1 |
b = 16.0908 (11) Å | T = 100 K |
c = 24.4828 (16) Å | 0.40 × 0.30 × 0.15 mm |
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 = 0.835 | Rint = 0.030 |
71530 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.070 | Δρmax = 0.29 e Å−3 |
S = 1.04 | Δρmin = −0.20 e Å−3 |
7427 reflections | Absolute structure: Flack (1983), with how many Friedel pairs? |
499 parameters | Absolute structure parameter: 0.028 (11) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
O1A | 1.03014 (11) | 0.18251 (6) | 0.08716 (4) | 0.0291 (3) | |
O2A | 0.80045 (10) | 0.46198 (6) | 0.11033 (4) | 0.0255 (3) | |
O3A | 0.96995 (10) | 0.46208 (6) | 0.16696 (4) | 0.0218 (3) | |
O4A | 1.28173 (10) | 0.17863 (6) | −0.00249 (4) | 0.0270 (3) | |
O5A | 1.13075 (10) | 0.12794 (6) | −0.05920 (4) | 0.0231 (3) | |
N1A | 1.09829 (11) | 0.29425 (7) | 0.03878 (4) | 0.0186 (3) | |
N2A | 0.98014 (11) | 0.29298 (7) | 0.17363 (4) | 0.0183 (3) | |
C1A | 1.07950 (13) | 0.25090 (8) | −0.01339 (5) | 0.0194 (3) | |
C2A | 1.10385 (14) | 0.31879 (8) | −0.05670 (5) | 0.0226 (4) | |
C3A | 1.07694 (13) | 0.39985 (8) | −0.02629 (6) | 0.0206 (4) | |
C4A | 1.13110 (13) | 0.47780 (8) | −0.05383 (6) | 0.0227 (4) | |
C5A | 1.27712 (13) | 0.48653 (8) | −0.04729 (6) | 0.0228 (4) | |
C6A | 1.31235 (13) | 0.48381 (9) | 0.01324 (6) | 0.0242 (4) | |
C7A | 1.27535 (13) | 0.39921 (8) | 0.03662 (5) | 0.0219 (4) | |
C8A | 1.13025 (13) | 0.38344 (8) | 0.03115 (5) | 0.0185 (3) | |
C9A | 1.07198 (13) | 0.25420 (8) | 0.08533 (6) | 0.0219 (4) | |
C10A | 1.09941 (13) | 0.29981 (8) | 0.13888 (5) | 0.0211 (4) | |
C11A | 0.86286 (13) | 0.33255 (8) | 0.14805 (5) | 0.0195 (4) | |
C12A | 0.74049 (14) | 0.31176 (9) | 0.18026 (6) | 0.0250 (4) | |
C13A | 0.72543 (15) | 0.35684 (10) | 0.23466 (6) | 0.0303 (4) | |
C14A | 0.59370 (18) | 0.33723 (14) | 0.26007 (8) | 0.0476 (6) | |
C15A | 1.17555 (13) | 0.18115 (8) | −0.02238 (5) | 0.0192 (4) | |
C16A | 1.21299 (15) | 0.25891 (10) | 0.16777 (6) | 0.0319 (4) | |
C17A | 0.88036 (13) | 0.42726 (8) | 0.14086 (5) | 0.0184 (3) | |
O1B | 0.96570 (10) | 0.12118 (6) | 0.44781 (4) | 0.0246 (3) | |
O2B | 1.18563 (11) | 0.32385 (6) | 0.33960 (4) | 0.0301 (3) | |
O3B | 1.03004 (10) | 0.28479 (6) | 0.28259 (4) | 0.0228 (3) | |
O4B | 0.71588 (9) | 0.19251 (7) | 0.52240 (4) | 0.0275 (3) | |
O5B | 0.86247 (10) | 0.20701 (7) | 0.58912 (4) | 0.0274 (3) | |
N1B | 0.89488 (11) | 0.25451 (7) | 0.44605 (4) | 0.0181 (3) | |
N2B | 0.99902 (11) | 0.13592 (7) | 0.33210 (5) | 0.0185 (3) | |
C1B | 0.91490 (13) | 0.26547 (8) | 0.50490 (5) | 0.0193 (4) | |
C2B | 0.89045 (14) | 0.35889 (8) | 0.51447 (6) | 0.0241 (4) | |
C3B | 0.91514 (13) | 0.39754 (8) | 0.45841 (6) | 0.0217 (4) | |
C4B | 0.86326 (14) | 0.48565 (8) | 0.45019 (6) | 0.0267 (4) | |
C5B | 0.71757 (15) | 0.48979 (9) | 0.44062 (7) | 0.0303 (4) | |
C6B | 0.67570 (14) | 0.42949 (9) | 0.39591 (6) | 0.0279 (4) | |
C7B | 0.71221 (13) | 0.34078 (8) | 0.41173 (6) | 0.0236 (4) | |
C8B | 0.85830 (12) | 0.33317 (8) | 0.41901 (5) | 0.0186 (3) | |
C9B | 0.92176 (12) | 0.18083 (8) | 0.42288 (5) | 0.0188 (3) | |
C10B | 0.88685 (13) | 0.17203 (8) | 0.36248 (5) | 0.0197 (3) | |
C11B | 1.12511 (14) | 0.18023 (8) | 0.33804 (5) | 0.0210 (3) | |
C12B | 1.22102 (14) | 0.13182 (9) | 0.30184 (6) | 0.0266 (4) | |
C13B | 1.35855 (15) | 0.16495 (10) | 0.30157 (7) | 0.0342 (5) | |
C14B | 1.44372 (17) | 0.11066 (13) | 0.26491 (9) | 0.0494 (6) | |
C15B | 0.81958 (13) | 0.21552 (8) | 0.53841 (5) | 0.0201 (3) | |
C16B | 0.76990 (15) | 0.11493 (9) | 0.35671 (6) | 0.0275 (4) | |
C17B | 1.11211 (13) | 0.27146 (7) | 0.31868 (5) | 0.0190 (3) | |
S1S | 0.88079 (4) | 0.05813 (2) | 0.18727 (1) | 0.0316 (1) | |
O1S | 0.90813 (11) | 0.13526 (6) | 0.22131 (4) | 0.0278 (3) | |
C1S | 1.01876 (17) | −0.00629 (10) | 0.19497 (7) | 0.0375 (5) | |
C2S | 0.77414 (18) | −0.00566 (12) | 0.22695 (10) | 0.0524 (7) | |
H2NA | 0.9647 (18) | 0.2390 (12) | 0.1817 (7) | 0.034 (5)* | |
H1A | 0.98910 | 0.22950 | −0.01630 | 0.0230* | |
H2NB | 0.9961 (16) | 0.3175 (11) | 0.2059 (7) | 0.023 (4)* | |
H2A | 1.04470 | 0.31220 | −0.08820 | 0.0270* | |
H2B | 1.19420 | 0.31690 | −0.07000 | 0.0270* | |
H5OA | 1.199 (2) | 0.0949 (14) | −0.0707 (8) | 0.048 (6)* | |
H3A | 0.98110 | 0.40650 | −0.02330 | 0.0250* | |
H4A | 1.10980 | 0.47610 | −0.09320 | 0.0270* | |
H4B | 1.08860 | 0.52740 | −0.03800 | 0.0270* | |
H5A | 1.32130 | 0.44080 | −0.06680 | 0.0270* | |
H5B | 1.30610 | 0.53980 | −0.06330 | 0.0270* | |
H6A | 1.40630 | 0.49310 | 0.01780 | 0.0290* | |
H6B | 1.26580 | 0.52830 | 0.03310 | 0.0290* | |
H7A | 1.32340 | 0.35510 | 0.01710 | 0.0260* | |
H7B | 1.30010 | 0.39680 | 0.07570 | 0.0260* | |
H8A | 1.08210 | 0.41780 | 0.05850 | 0.0220* | |
H10A | 1.11920 | 0.35960 | 0.13140 | 0.0250* | |
H11A | 0.85270 | 0.30800 | 0.11080 | 0.0230* | |
H12A | 0.66470 | 0.32490 | 0.15720 | 0.0300* | |
H12B | 0.73930 | 0.25120 | 0.18730 | 0.0300* | |
H13A | 0.73330 | 0.41750 | 0.22880 | 0.0360* | |
H13B | 0.79500 | 0.33930 | 0.25990 | 0.0360* | |
H14A | 0.52500 | 0.35410 | 0.23490 | 0.0710* | |
H14B | 0.58450 | 0.36760 | 0.29450 | 0.0710* | |
H14C | 0.58730 | 0.27740 | 0.26710 | 0.0710* | |
H16A | 1.22700 | 0.28590 | 0.20320 | 0.0480* | |
H16B | 1.29080 | 0.26460 | 0.14530 | 0.0480* | |
H16C | 1.19430 | 0.19980 | 0.17350 | 0.0480* | |
H1B | 1.00560 | 0.25060 | 0.51510 | 0.0230* | |
H2C | 0.80060 | 0.36900 | 0.52660 | 0.0290* | |
H2D | 0.95070 | 0.38150 | 0.54210 | 0.0290* | |
H3B | 1.01070 | 0.39910 | 0.45250 | 0.0260* | |
H2NC | 1.0070 (18) | 0.0844 (12) | 0.3401 (7) | 0.029 (4)* | |
H4C | 0.90780 | 0.51100 | 0.41850 | 0.0320* | |
H4D | 0.88470 | 0.51920 | 0.48280 | 0.0320* | |
H2ND | 0.9786 (17) | 0.1364 (11) | 0.2969 (8) | 0.023 (4)* | |
H5C | 0.69330 | 0.54710 | 0.43000 | 0.0360* | |
H5D | 0.67180 | 0.47610 | 0.47500 | 0.0360* | |
H5OB | 0.803 (2) | 0.1953 (14) | 0.6081 (9) | 0.051 (6)* | |
H6C | 0.58110 | 0.43330 | 0.39060 | 0.0330* | |
H6D | 0.71830 | 0.44450 | 0.36110 | 0.0330* | |
H7C | 0.68300 | 0.30190 | 0.38290 | 0.0280* | |
H7D | 0.66830 | 0.32550 | 0.44620 | 0.0280* | |
H8B | 0.90210 | 0.33740 | 0.38270 | 0.0220* | |
H10B | 0.86560 | 0.22800 | 0.34710 | 0.0240* | |
H11B | 1.15410 | 0.17860 | 0.37700 | 0.0250* | |
H12C | 1.22290 | 0.07330 | 0.31430 | 0.0320* | |
H12D | 1.18810 | 0.13210 | 0.26390 | 0.0320* | |
H13C | 1.39330 | 0.16500 | 0.33920 | 0.0410* | |
H13D | 1.35900 | 0.22290 | 0.28790 | 0.0410* | |
H14D | 1.44150 | 0.05310 | 0.27800 | 0.0740* | |
H14E | 1.53280 | 0.13130 | 0.26600 | 0.0740* | |
H14F | 1.41140 | 0.11290 | 0.22730 | 0.0740* | |
H16D | 0.74410 | 0.11210 | 0.31820 | 0.0410* | |
H16E | 0.69820 | 0.13690 | 0.37850 | 0.0410* | |
H16F | 0.79230 | 0.05910 | 0.36970 | 0.0410* | |
H1S1 | 1.09370 | 0.02070 | 0.17820 | 0.0560* | |
H1S2 | 1.00310 | −0.05980 | 0.17710 | 0.0560* | |
H1S3 | 1.03560 | −0.01530 | 0.23390 | 0.0560* | |
H2S1 | 0.81140 | −0.01460 | 0.26330 | 0.0790* | |
H2S2 | 0.76250 | −0.05930 | 0.20870 | 0.0790* | |
H2S3 | 0.69030 | 0.02210 | 0.23050 | 0.0790* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0417 (6) | 0.0174 (5) | 0.0281 (5) | −0.0044 (4) | 0.0080 (5) | −0.0004 (4) |
O2A | 0.0336 (5) | 0.0176 (5) | 0.0254 (5) | 0.0003 (4) | −0.0075 (4) | 0.0010 (4) |
O3A | 0.0256 (5) | 0.0168 (4) | 0.0230 (5) | −0.0020 (4) | −0.0007 (4) | −0.0012 (4) |
O4A | 0.0235 (5) | 0.0234 (5) | 0.0340 (5) | 0.0034 (4) | −0.0013 (4) | −0.0025 (4) |
O5A | 0.0283 (5) | 0.0188 (4) | 0.0221 (5) | 0.0003 (4) | 0.0041 (4) | −0.0027 (4) |
N1A | 0.0205 (5) | 0.0150 (5) | 0.0202 (5) | 0.0002 (4) | 0.0019 (4) | −0.0013 (4) |
N2A | 0.0240 (6) | 0.0139 (5) | 0.0169 (5) | −0.0002 (4) | −0.0003 (4) | 0.0015 (4) |
C1A | 0.0193 (6) | 0.0192 (6) | 0.0197 (6) | −0.0026 (5) | 0.0001 (5) | −0.0001 (5) |
C2A | 0.0284 (7) | 0.0189 (6) | 0.0205 (6) | −0.0007 (5) | −0.0037 (5) | 0.0015 (5) |
C3A | 0.0174 (6) | 0.0188 (7) | 0.0255 (7) | 0.0010 (5) | −0.0004 (5) | 0.0017 (5) |
C4A | 0.0251 (7) | 0.0175 (6) | 0.0254 (7) | 0.0027 (5) | −0.0005 (6) | 0.0030 (5) |
C5A | 0.0262 (7) | 0.0196 (6) | 0.0225 (7) | −0.0020 (5) | 0.0049 (5) | 0.0015 (5) |
C6A | 0.0232 (7) | 0.0247 (7) | 0.0247 (7) | −0.0068 (6) | 0.0021 (5) | −0.0013 (6) |
C7A | 0.0212 (6) | 0.0230 (7) | 0.0215 (6) | −0.0013 (5) | −0.0021 (5) | 0.0016 (5) |
C8A | 0.0199 (6) | 0.0141 (6) | 0.0215 (6) | 0.0008 (5) | 0.0034 (5) | −0.0002 (5) |
C9A | 0.0222 (6) | 0.0183 (6) | 0.0252 (7) | 0.0027 (5) | 0.0037 (5) | −0.0007 (5) |
C10A | 0.0239 (7) | 0.0195 (6) | 0.0199 (6) | 0.0000 (5) | 0.0028 (5) | 0.0022 (5) |
C11A | 0.0237 (7) | 0.0162 (6) | 0.0187 (6) | 0.0003 (5) | −0.0022 (5) | 0.0009 (5) |
C12A | 0.0259 (7) | 0.0221 (7) | 0.0270 (7) | −0.0021 (5) | −0.0002 (6) | 0.0033 (6) |
C13A | 0.0283 (7) | 0.0365 (8) | 0.0261 (7) | −0.0035 (6) | −0.0006 (6) | 0.0000 (6) |
C14A | 0.0368 (9) | 0.0666 (12) | 0.0395 (9) | −0.0113 (9) | 0.0120 (8) | −0.0100 (9) |
C15A | 0.0233 (7) | 0.0158 (6) | 0.0185 (6) | −0.0039 (5) | 0.0049 (5) | 0.0036 (5) |
C16A | 0.0271 (7) | 0.0371 (8) | 0.0316 (8) | 0.0055 (6) | −0.0003 (6) | 0.0031 (6) |
C17A | 0.0234 (6) | 0.0161 (6) | 0.0158 (6) | −0.0002 (5) | 0.0031 (5) | −0.0012 (5) |
O1B | 0.0325 (5) | 0.0200 (5) | 0.0213 (5) | 0.0053 (4) | 0.0020 (4) | 0.0024 (4) |
O2B | 0.0406 (6) | 0.0184 (5) | 0.0314 (5) | −0.0030 (4) | −0.0150 (5) | 0.0034 (4) |
O3B | 0.0306 (5) | 0.0187 (5) | 0.0192 (4) | −0.0007 (4) | −0.0051 (4) | 0.0028 (4) |
O4B | 0.0216 (5) | 0.0293 (5) | 0.0317 (5) | −0.0034 (4) | 0.0011 (4) | 0.0042 (4) |
O5B | 0.0285 (5) | 0.0344 (6) | 0.0194 (5) | −0.0043 (4) | 0.0043 (4) | 0.0017 (4) |
N1B | 0.0196 (5) | 0.0181 (5) | 0.0167 (5) | 0.0001 (4) | 0.0016 (4) | −0.0005 (4) |
N2B | 0.0280 (6) | 0.0124 (5) | 0.0150 (5) | 0.0031 (4) | 0.0024 (4) | 0.0016 (4) |
C1B | 0.0183 (6) | 0.0222 (7) | 0.0175 (6) | −0.0002 (5) | −0.0003 (5) | −0.0025 (5) |
C2B | 0.0284 (7) | 0.0213 (7) | 0.0227 (7) | −0.0036 (6) | 0.0009 (6) | −0.0047 (5) |
C3B | 0.0192 (6) | 0.0196 (7) | 0.0264 (7) | −0.0020 (5) | 0.0030 (5) | −0.0021 (5) |
C4B | 0.0312 (7) | 0.0178 (6) | 0.0310 (7) | −0.0002 (6) | 0.0029 (6) | −0.0036 (5) |
C5B | 0.0300 (7) | 0.0228 (7) | 0.0381 (8) | 0.0078 (6) | 0.0047 (6) | −0.0039 (6) |
C6B | 0.0215 (7) | 0.0254 (7) | 0.0367 (8) | 0.0059 (6) | 0.0003 (6) | −0.0002 (6) |
C7B | 0.0207 (6) | 0.0215 (7) | 0.0286 (7) | −0.0002 (5) | 0.0003 (6) | −0.0010 (5) |
C8B | 0.0201 (6) | 0.0156 (6) | 0.0200 (6) | 0.0005 (5) | 0.0035 (5) | 0.0004 (5) |
C9B | 0.0183 (6) | 0.0183 (6) | 0.0197 (6) | −0.0009 (5) | 0.0036 (5) | 0.0010 (5) |
C10B | 0.0239 (6) | 0.0159 (6) | 0.0194 (6) | 0.0028 (5) | 0.0018 (5) | −0.0011 (5) |
C11B | 0.0226 (6) | 0.0194 (6) | 0.0210 (6) | 0.0015 (5) | 0.0015 (5) | 0.0038 (5) |
C12B | 0.0292 (7) | 0.0211 (7) | 0.0295 (7) | 0.0023 (6) | 0.0017 (6) | 0.0019 (6) |
C13B | 0.0253 (8) | 0.0350 (8) | 0.0422 (9) | 0.0019 (6) | 0.0015 (7) | −0.0048 (7) |
C14B | 0.0291 (8) | 0.0518 (12) | 0.0674 (13) | 0.0071 (8) | 0.0099 (8) | −0.0146 (10) |
C15B | 0.0197 (6) | 0.0182 (6) | 0.0225 (6) | 0.0026 (5) | 0.0037 (5) | −0.0014 (5) |
C16B | 0.0293 (7) | 0.0284 (7) | 0.0248 (7) | −0.0036 (6) | 0.0005 (6) | −0.0039 (6) |
C17B | 0.0257 (6) | 0.0152 (6) | 0.0162 (6) | 0.0024 (5) | 0.0032 (5) | 0.0009 (5) |
S1S | 0.0490 (2) | 0.0204 (2) | 0.0254 (2) | 0.0019 (2) | −0.0118 (2) | −0.0054 (1) |
O1S | 0.0446 (6) | 0.0162 (5) | 0.0227 (5) | 0.0009 (4) | −0.0051 (4) | −0.0009 (4) |
C1S | 0.0400 (9) | 0.0282 (8) | 0.0442 (9) | 0.0023 (7) | 0.0102 (8) | −0.0111 (7) |
C2S | 0.0387 (9) | 0.0338 (9) | 0.0847 (15) | −0.0119 (8) | 0.0198 (10) | −0.0296 (10) |
S1S—C2S | 1.793 (2) | C11A—H11A | 1.0000 |
S1S—O1S | 1.5215 (10) | C12A—H12B | 0.9900 |
S1S—C1S | 1.7746 (18) | C12A—H12A | 0.9900 |
O1A—C9A | 1.2330 (16) | C13A—H13A | 0.9900 |
O2A—C17A | 1.2470 (16) | C13A—H13B | 0.9900 |
O3A—C17A | 1.2578 (16) | C14A—H14B | 0.9800 |
O4A—C15A | 1.2027 (17) | C14A—H14A | 0.9800 |
O5A—C15A | 1.3269 (16) | C14A—H14C | 0.9800 |
O5A—H5OA | 0.93 (2) | C16A—H16C | 0.9800 |
O1B—C9B | 1.2250 (16) | C16A—H16B | 0.9800 |
O2B—C17B | 1.2458 (16) | C16A—H16A | 0.9800 |
O3B—C17B | 1.2443 (16) | C1B—C15B | 1.5141 (18) |
O4B—C15B | 1.2012 (16) | C1B—C2B | 1.5423 (18) |
O5B—C15B | 1.3256 (16) | C2B—C3B | 1.528 (2) |
O5B—H5OB | 0.79 (2) | C3B—C8B | 1.5328 (19) |
N1A—C8A | 1.4846 (17) | C3B—C4B | 1.5293 (18) |
N1A—C1A | 1.4683 (16) | C4B—C5B | 1.528 (2) |
N1A—C9A | 1.3373 (18) | C5B—C6B | 1.526 (2) |
N2A—C11A | 1.5070 (17) | C6B—C7B | 1.527 (2) |
N2A—C10A | 1.5033 (17) | C7B—C8B | 1.5275 (18) |
N2A—H2NA | 0.905 (19) | C9B—C10B | 1.5288 (17) |
N2A—H2NB | 0.898 (17) | C10B—C16B | 1.526 (2) |
N1B—C1B | 1.4663 (16) | C11B—C12B | 1.542 (2) |
N1B—C9B | 1.3434 (17) | C11B—C17B | 1.5485 (17) |
N1B—C8B | 1.4777 (17) | C12B—C13B | 1.520 (2) |
N2B—C10B | 1.4963 (18) | C13B—C14B | 1.532 (3) |
N2B—C11B | 1.4942 (18) | C1B—H1B | 1.0000 |
N2B—H2ND | 0.887 (19) | C2B—H2C | 0.9900 |
N2B—H2NC | 0.856 (19) | C2B—H2D | 0.9900 |
C1A—C2A | 1.5431 (18) | C3B—H3B | 1.0000 |
C1A—C15A | 1.5154 (19) | C4B—H4D | 0.9900 |
C2A—C3A | 1.5275 (19) | C4B—H4C | 0.9900 |
C3A—C8A | 1.5336 (19) | C5B—H5C | 0.9900 |
C3A—C4A | 1.5304 (19) | C5B—H5D | 0.9900 |
C4A—C5A | 1.5263 (19) | C6B—H6C | 0.9900 |
C5A—C6A | 1.527 (2) | C6B—H6D | 0.9900 |
C6A—C7A | 1.5256 (19) | C7B—H7D | 0.9900 |
C7A—C8A | 1.5290 (19) | C7B—H7C | 0.9900 |
C9A—C10A | 1.5291 (19) | C8B—H8B | 1.0000 |
C10A—C16A | 1.522 (2) | C10B—H10B | 1.0000 |
C11A—C17A | 1.5448 (18) | C11B—H11B | 1.0000 |
C11A—C12A | 1.529 (2) | C12B—H12C | 0.9900 |
C12A—C13A | 1.525 (2) | C12B—H12D | 0.9900 |
C13A—C14A | 1.532 (2) | C13B—H13C | 0.9900 |
C1A—H1A | 1.0000 | C13B—H13D | 0.9900 |
C2A—H2B | 0.9900 | C14B—H14F | 0.9800 |
C2A—H2A | 0.9900 | C14B—H14D | 0.9800 |
C3A—H3A | 1.0000 | C14B—H14E | 0.9800 |
C4A—H4B | 0.9900 | C16B—H16D | 0.9800 |
C4A—H4A | 0.9900 | C16B—H16E | 0.9800 |
C5A—H5B | 0.9900 | C16B—H16F | 0.9800 |
C5A—H5A | 0.9900 | C1S—H1S1 | 0.9800 |
C6A—H6B | 0.9900 | C1S—H1S2 | 0.9800 |
C6A—H6A | 0.9900 | C1S—H1S3 | 0.9800 |
C7A—H7B | 0.9900 | C2S—H2S1 | 0.9800 |
C7A—H7A | 0.9900 | C2S—H2S2 | 0.9800 |
C8A—H8A | 1.0000 | C2S—H2S3 | 0.9800 |
C10A—H10A | 1.0000 | ||
C1S—S1S—C2S | 95.94 (8) | H16A—C16A—H16C | 109.00 |
O1S—S1S—C1S | 105.58 (7) | C10A—C16A—H16A | 109.00 |
O1S—S1S—C2S | 106.54 (8) | C10A—C16A—H16B | 109.00 |
C15A—O5A—H5OA | 108.1 (13) | H16A—C16A—H16B | 109.00 |
C15B—O5B—H5OB | 108.2 (16) | C10A—C16A—H16C | 109.00 |
C1A—N1A—C8A | 112.29 (9) | N1B—C1B—C2B | 104.08 (10) |
C1A—N1A—C9A | 119.04 (11) | N1B—C1B—C15B | 112.12 (11) |
C8A—N1A—C9A | 128.20 (11) | C2B—C1B—C15B | 109.16 (11) |
C10A—N2A—C11A | 113.29 (9) | C1B—C2B—C3B | 103.46 (11) |
C10A—N2A—H2NA | 109.8 (12) | C2B—C3B—C4B | 115.89 (12) |
C11A—N2A—H2NA | 110.7 (12) | C2B—C3B—C8B | 103.06 (10) |
C11A—N2A—H2NB | 109.2 (11) | C4B—C3B—C8B | 114.13 (11) |
C10A—N2A—H2NB | 108.3 (11) | C3B—C4B—C5B | 114.03 (11) |
H2NA—N2A—H2NB | 105.2 (16) | C4B—C5B—C6B | 111.27 (12) |
C1B—N1B—C9B | 119.46 (11) | C5B—C6B—C7B | 110.02 (12) |
C8B—N1B—C9B | 128.30 (10) | C6B—C7B—C8B | 110.46 (11) |
C1B—N1B—C8B | 111.93 (10) | N1B—C8B—C7B | 112.00 (10) |
C10B—N2B—C11B | 116.36 (10) | N1B—C8B—C3B | 101.45 (10) |
C11B—N2B—H2NC | 110.8 (12) | C3B—C8B—C7B | 113.53 (11) |
C11B—N2B—H2ND | 107.4 (12) | O1B—C9B—C10B | 119.81 (11) |
C10B—N2B—H2ND | 107.1 (12) | O1B—C9B—N1B | 123.92 (12) |
C10B—N2B—H2NC | 109.7 (12) | N1B—C9B—C10B | 116.18 (11) |
H2NC—N2B—H2ND | 104.7 (16) | N2B—C10B—C16B | 109.61 (11) |
C2A—C1A—C15A | 108.50 (10) | C9B—C10B—C16B | 109.44 (11) |
N1A—C1A—C2A | 103.88 (10) | N2B—C10B—C9B | 109.48 (10) |
N1A—C1A—C15A | 113.04 (10) | N2B—C11B—C17B | 110.28 (11) |
C1A—C2A—C3A | 103.87 (10) | C12B—C11B—C17B | 111.03 (11) |
C2A—C3A—C4A | 114.73 (12) | N2B—C11B—C12B | 105.39 (10) |
C2A—C3A—C8A | 103.55 (10) | C11B—C12B—C13B | 115.36 (12) |
C4A—C3A—C8A | 114.41 (11) | C12B—C13B—C14B | 109.97 (13) |
C3A—C4A—C5A | 113.07 (11) | O4B—C15B—C1B | 124.69 (12) |
C4A—C5A—C6A | 109.61 (11) | O5B—C15B—C1B | 110.13 (11) |
C5A—C6A—C7A | 109.26 (11) | O4B—C15B—O5B | 124.96 (12) |
C6A—C7A—C8A | 111.21 (11) | O3B—C17B—C11B | 116.11 (11) |
N1A—C8A—C7A | 111.61 (11) | O2B—C17B—O3B | 126.32 (11) |
C3A—C8A—C7A | 113.90 (11) | O2B—C17B—C11B | 117.55 (11) |
N1A—C8A—C3A | 101.63 (10) | C2B—C1B—H1B | 110.00 |
O1A—C9A—C10A | 118.89 (12) | N1B—C1B—H1B | 110.00 |
O1A—C9A—N1A | 123.60 (13) | C15B—C1B—H1B | 110.00 |
N1A—C9A—C10A | 117.49 (11) | C3B—C2B—H2C | 111.00 |
C9A—C10A—C16A | 109.54 (11) | C1B—C2B—H2D | 111.00 |
N2A—C10A—C16A | 109.86 (10) | C1B—C2B—H2C | 111.00 |
N2A—C10A—C9A | 107.32 (10) | C3B—C2B—H2D | 111.00 |
N2A—C11A—C17A | 111.70 (10) | H2C—C2B—H2D | 109.00 |
C12A—C11A—C17A | 111.82 (11) | C2B—C3B—H3B | 108.00 |
N2A—C11A—C12A | 111.13 (10) | C4B—C3B—H3B | 108.00 |
C11A—C12A—C13A | 115.54 (12) | C8B—C3B—H3B | 108.00 |
C12A—C13A—C14A | 110.36 (13) | C3B—C4B—H4D | 109.00 |
O5A—C15A—C1A | 110.32 (11) | H4C—C4B—H4D | 108.00 |
O4A—C15A—O5A | 124.93 (12) | C5B—C4B—H4C | 109.00 |
O4A—C15A—C1A | 124.45 (12) | C5B—C4B—H4D | 109.00 |
O2A—C17A—O3A | 126.44 (12) | C3B—C4B—H4C | 109.00 |
O3A—C17A—C11A | 117.90 (11) | C6B—C5B—H5D | 109.00 |
O2A—C17A—C11A | 115.63 (11) | H5C—C5B—H5D | 108.00 |
C15A—C1A—H1A | 110.00 | C4B—C5B—H5C | 109.00 |
C2A—C1A—H1A | 110.00 | C4B—C5B—H5D | 109.00 |
N1A—C1A—H1A | 110.00 | C6B—C5B—H5C | 109.00 |
C1A—C2A—H2B | 111.00 | C5B—C6B—H6C | 110.00 |
C3A—C2A—H2A | 111.00 | C5B—C6B—H6D | 110.00 |
C3A—C2A—H2B | 111.00 | C7B—C6B—H6C | 110.00 |
H2A—C2A—H2B | 109.00 | C7B—C6B—H6D | 110.00 |
C1A—C2A—H2A | 111.00 | H6C—C6B—H6D | 108.00 |
C2A—C3A—H3A | 108.00 | C6B—C7B—H7D | 110.00 |
C8A—C3A—H3A | 108.00 | H7C—C7B—H7D | 108.00 |
C4A—C3A—H3A | 108.00 | C8B—C7B—H7C | 110.00 |
C5A—C4A—H4A | 109.00 | C8B—C7B—H7D | 110.00 |
H4A—C4A—H4B | 108.00 | C6B—C7B—H7C | 110.00 |
C3A—C4A—H4B | 109.00 | C7B—C8B—H8B | 110.00 |
C3A—C4A—H4A | 109.00 | C3B—C8B—H8B | 110.00 |
C5A—C4A—H4B | 109.00 | N1B—C8B—H8B | 110.00 |
H5A—C5A—H5B | 108.00 | C16B—C10B—H10B | 109.00 |
C6A—C5A—H5B | 110.00 | C9B—C10B—H10B | 109.00 |
C4A—C5A—H5A | 110.00 | N2B—C10B—H10B | 109.00 |
C4A—C5A—H5B | 110.00 | N2B—C11B—H11B | 110.00 |
C6A—C5A—H5A | 110.00 | C12B—C11B—H11B | 110.00 |
C5A—C6A—H6B | 110.00 | C17B—C11B—H11B | 110.00 |
C7A—C6A—H6A | 110.00 | C13B—C12B—H12D | 108.00 |
C5A—C6A—H6A | 110.00 | H12C—C12B—H12D | 107.00 |
H6A—C6A—H6B | 108.00 | C11B—C12B—H12D | 108.00 |
C7A—C6A—H6B | 110.00 | C13B—C12B—H12C | 108.00 |
C8A—C7A—H7A | 109.00 | C11B—C12B—H12C | 108.00 |
H7A—C7A—H7B | 108.00 | C12B—C13B—H13C | 110.00 |
C6A—C7A—H7B | 109.00 | C12B—C13B—H13D | 110.00 |
C6A—C7A—H7A | 109.00 | H13C—C13B—H13D | 108.00 |
C8A—C7A—H7B | 109.00 | C14B—C13B—H13C | 110.00 |
N1A—C8A—H8A | 110.00 | C14B—C13B—H13D | 110.00 |
C7A—C8A—H8A | 110.00 | C13B—C14B—H14E | 109.00 |
C3A—C8A—H8A | 110.00 | H14D—C14B—H14F | 109.00 |
N2A—C10A—H10A | 110.00 | C13B—C14B—H14F | 109.00 |
C9A—C10A—H10A | 110.00 | H14D—C14B—H14E | 109.00 |
C16A—C10A—H10A | 110.00 | C13B—C14B—H14D | 109.00 |
C17A—C11A—H11A | 107.00 | H14E—C14B—H14F | 110.00 |
N2A—C11A—H11A | 107.00 | C10B—C16B—H16F | 110.00 |
C12A—C11A—H11A | 107.00 | H16D—C16B—H16F | 109.00 |
C13A—C12A—H12B | 108.00 | H16E—C16B—H16F | 109.00 |
H12A—C12A—H12B | 107.00 | H16D—C16B—H16E | 110.00 |
C11A—C12A—H12B | 108.00 | C10B—C16B—H16D | 109.00 |
C13A—C12A—H12A | 108.00 | C10B—C16B—H16E | 109.00 |
C11A—C12A—H12A | 108.00 | S1S—C1S—H1S1 | 110.00 |
C12A—C13A—H13B | 110.00 | S1S—C1S—H1S2 | 109.00 |
C12A—C13A—H13A | 110.00 | S1S—C1S—H1S3 | 109.00 |
C14A—C13A—H13B | 110.00 | H1S1—C1S—H1S2 | 109.00 |
H13A—C13A—H13B | 108.00 | H1S1—C1S—H1S3 | 109.00 |
C14A—C13A—H13A | 110.00 | H1S2—C1S—H1S3 | 110.00 |
C13A—C14A—H14C | 110.00 | S1S—C2S—H2S1 | 109.00 |
H14A—C14A—H14B | 109.00 | S1S—C2S—H2S2 | 109.00 |
C13A—C14A—H14A | 109.00 | S1S—C2S—H2S3 | 109.00 |
C13A—C14A—H14B | 109.00 | H2S1—C2S—H2S2 | 109.00 |
H14B—C14A—H14C | 109.00 | H2S1—C2S—H2S3 | 110.00 |
H14A—C14A—H14C | 109.00 | H2S2—C2S—H2S3 | 109.00 |
H16B—C16A—H16C | 109.00 | ||
C8A—N1A—C1A—C2A | 0.85 (14) | C3A—C4A—C5A—C6A | −55.15 (15) |
C9A—N1A—C1A—C2A | 173.69 (12) | C4A—C5A—C6A—C7A | 63.12 (14) |
C8A—N1A—C1A—C15A | 118.25 (12) | C5A—C6A—C7A—C8A | −60.44 (14) |
C9A—N1A—C1A—C15A | −68.91 (15) | C6A—C7A—C8A—N1A | 163.84 (10) |
C9A—N1A—C8A—C7A | 88.24 (16) | C6A—C7A—C8A—C3A | 49.46 (14) |
C1A—N1A—C9A—O1A | −1.3 (2) | N1A—C9A—C10A—N2A | 130.27 (12) |
C8A—N1A—C9A—O1A | 170.23 (13) | N1A—C9A—C10A—C16A | −110.51 (14) |
C1A—N1A—C9A—C10A | 176.89 (11) | O1A—C9A—C10A—N2A | −51.42 (16) |
C1A—N1A—C8A—C3A | 22.03 (13) | O1A—C9A—C10A—C16A | 67.80 (16) |
C9A—N1A—C8A—C3A | −149.99 (13) | N2A—C11A—C12A—C13A | 73.78 (15) |
C1A—N1A—C8A—C7A | −99.73 (12) | C17A—C11A—C12A—C13A | −51.79 (16) |
C8A—N1A—C9A—C10A | −11.6 (2) | N2A—C11A—C17A—O2A | 165.97 (11) |
C11A—N2A—C10A—C9A | −61.32 (13) | N2A—C11A—C17A—O3A | −15.88 (16) |
C10A—N2A—C11A—C12A | 170.73 (10) | C12A—C11A—C17A—O2A | −68.77 (15) |
C10A—N2A—C11A—C17A | −63.63 (13) | C12A—C11A—C17A—O3A | 109.37 (14) |
C11A—N2A—C10A—C16A | 179.66 (11) | C11A—C12A—C13A—C14A | 174.49 (13) |
C9B—N1B—C1B—C2B | 173.21 (11) | C2B—C1B—C15B—O4B | 91.23 (16) |
C8B—N1B—C1B—C15B | 116.98 (12) | C2B—C1B—C15B—O5B | −83.55 (13) |
C9B—N1B—C1B—C15B | −68.94 (15) | C15B—C1B—C2B—C3B | −143.16 (11) |
C8B—N1B—C9B—O1B | 171.23 (12) | N1B—C1B—C15B—O4B | −23.56 (18) |
C1B—N1B—C9B—C10B | 174.67 (11) | N1B—C1B—C2B—C3B | −23.28 (13) |
C8B—N1B—C9B—C10B | −12.33 (19) | N1B—C1B—C15B—O5B | 161.66 (11) |
C1B—N1B—C8B—C3B | 24.39 (13) | C1B—C2B—C3B—C8B | 38.26 (13) |
C1B—N1B—C8B—C7B | −97.02 (13) | C1B—C2B—C3B—C4B | 163.66 (11) |
C9B—N1B—C8B—C7B | 89.55 (15) | C4B—C3B—C8B—N1B | −164.47 (11) |
C1B—N1B—C9B—O1B | −1.77 (19) | C8B—C3B—C4B—C5B | 42.71 (17) |
C8B—N1B—C1B—C2B | −0.87 (14) | C2B—C3B—C8B—N1B | −37.95 (12) |
C9B—N1B—C8B—C3B | −149.04 (13) | C2B—C3B—C4B—C5B | −76.82 (16) |
C11B—N2B—C10B—C16B | −174.36 (11) | C4B—C3B—C8B—C7B | −44.14 (16) |
C10B—N2B—C11B—C12B | −178.55 (11) | C2B—C3B—C8B—C7B | 82.39 (13) |
C10B—N2B—C11B—C17B | −58.64 (14) | C3B—C4B—C5B—C6B | −50.34 (17) |
C11B—N2B—C10B—C9B | −54.31 (14) | C4B—C5B—C6B—C7B | 59.21 (16) |
C15A—C1A—C2A—C3A | −144.21 (11) | C5B—C6B—C7B—C8B | −60.49 (15) |
N1A—C1A—C15A—O5A | 159.42 (11) | C6B—C7B—C8B—N1B | 167.19 (11) |
C2A—C1A—C15A—O4A | 88.05 (15) | C6B—C7B—C8B—C3B | 53.02 (15) |
N1A—C1A—C2A—C3A | −23.70 (13) | O1B—C9B—C10B—C16B | 68.75 (15) |
N1A—C1A—C15A—O4A | −26.61 (18) | N1B—C9B—C10B—N2B | 132.01 (12) |
C2A—C1A—C15A—O5A | −85.93 (13) | N1B—C9B—C10B—C16B | −107.84 (13) |
C1A—C2A—C3A—C8A | 37.43 (13) | O1B—C9B—C10B—N2B | −51.40 (16) |
C1A—C2A—C3A—C4A | 162.82 (11) | N2B—C11B—C12B—C13B | −179.38 (12) |
C2A—C3A—C4A—C5A | −75.11 (15) | C17B—C11B—C12B—C13B | 61.22 (16) |
C2A—C3A—C8A—C7A | 84.21 (13) | N2B—C11B—C17B—O2B | 152.26 (12) |
C4A—C3A—C8A—N1A | −161.54 (11) | N2B—C11B—C17B—O3B | −29.14 (15) |
C2A—C3A—C8A—N1A | −35.96 (12) | C12B—C11B—C17B—O2B | −91.31 (14) |
C4A—C3A—C8A—C7A | −41.38 (15) | C12B—C11B—C17B—O3B | 87.30 (15) |
C8A—C3A—C4A—C5A | 44.39 (16) | C11B—C12B—C13B—C14B | 179.11 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2A—H2NA···O1S | 0.905 (19) | 2.017 (19) | 2.8912 (15) | 161.9 (16) |
N2A—H2NB···O3B | 0.898 (17) | 1.981 (17) | 2.7204 (14) | 138.5 (15) |
O5A—H5OA···O2Ai | 0.93 (2) | 1.70 (2) | 2.5972 (14) | 162.4 (19) |
N2B—H2NC···O3Aii | 0.856 (19) | 1.990 (19) | 2.8157 (15) | 161.8 (16) |
N2B—H2ND···O1S | 0.887 (19) | 1.989 (19) | 2.8710 (16) | 172.2 (17) |
O5B—H5OB···O2Biii | 0.79 (2) | 1.79 (2) | 2.5773 (15) | 170 (2) |
C1B—H1B···O4Biv | 1.00 | 2.53 | 3.2571 (17) | 129 |
C3A—H3A···O4Av | 1.00 | 2.56 | 3.3805 (17) | 140 |
C4B—H4D···O5Avi | 0.99 | 2.57 | 3.5169 (17) | 161 |
C1S—H1S3···O3Aii | 0.98 | 2.46 | 3.420 (2) | 168 |
C10A—H10A···O3A | 1.00 | 2.42 | 3.0143 (16) | 117 |
C10B—H10B···O3B | 1.00 | 2.50 | 3.0519 (16) | 115 |
C2S—H2S2···O2Bii | 0.98 | 2.29 | 3.218 (2) | 159 |
C12A—H12A···O5Av | 0.99 | 2.54 | 3.3191 (18) | 135 |
C12B—H12C···O2Aii | 0.99 | 2.58 | 3.4845 (18) | 151 |
Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) −x+2, y−1/2, −z+1/2; (iii) x−1/2, −y+1/2, −z+1; (iv) x+1/2, −y+1/2, −z+1; (v) x−1/2, −y+1/2, −z; (vi) −x+2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C17H28N2O5·0.5C2H6OS |
Mr | 379.49 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 10.3504 (7), 16.0908 (11), 24.4828 (16) |
V (Å3) | 4077.5 (5) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 1.21 |
Crystal size (mm) | 0.40 × 0.30 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.680, 0.835 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 71530, 7427, 7382 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.601 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.070, 1.04 |
No. of reflections | 7427 |
No. of parameters | 499 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.20 |
Absolute structure | Flack (1983), with how many Friedel pairs? |
Absolute structure parameter | 0.028 (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).
D—H···A | D—H | H···A | D···A | D—H···A |
N2A—H2NA···O1S | 0.905 (19) | 2.017 (19) | 2.8912 (15) | 161.9 (16) |
N2A—H2NB···O3B | 0.898 (17) | 1.981 (17) | 2.7204 (14) | 138.5 (15) |
O5A—H5OA···O2Ai | 0.93 (2) | 1.70 (2) | 2.5972 (14) | 162.4 (19) |
N2B—H2NC···O3Aii | 0.856 (19) | 1.990 (19) | 2.8157 (15) | 161.8 (16) |
N2B—H2ND···O1S | 0.887 (19) | 1.989 (19) | 2.8710 (16) | 172.2 (17) |
O5B—H5OB···O2Biii | 0.79 (2) | 1.79 (2) | 2.5773 (15) | 170 (2) |
Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) −x+2, y−1/2, −z+1/2; (iii) x−1/2, −y+1/2, −z+1. |
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°.