Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680705221X/wn2209sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680705221X/wn2209Isup2.hkl |
CCDC reference: 667440
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.003 Å
- R factor = 0.065
- wR factor = 0.166
- Data-to-parameter ratio = 19.9
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT413_ALERT_2_B Short Inter XH3 .. XHn H20D .. H22C .. 2.06 Ang.
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 200 Deg. PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.12 Ratio
Alert level G PLAT793_ALERT_1_G Check the Absolute Configuration of C2A = ... R PLAT793_ALERT_1_G Check the Absolute Configuration of C2B = ... R PLAT793_ALERT_1_G Check the Absolute Configuration of C3A = ... S PLAT793_ALERT_1_G Check the Absolute Configuration of C3B = ... S PLAT793_ALERT_1_G Check the Absolute Configuration of C4A = ... S PLAT793_ALERT_1_G Check the Absolute Configuration of C4B = ... S
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 6 ALERT level G = General alerts; check 8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
To a solution of 1,3-dimethylpyrimidine-2,4,6-trione (1 mmol) in dry toluene (20 ml), 2-[N-(3-methylbut-2-enyl)-N-tosylamino]butanal (1 mmol) and a catalytic amount of the base ethylenediamine-N,N'-diacetate (EDDA) were added and the reaction mixture was refluxed for 12 h. After completion of the reaction, the solvent was evaporated under reduced pressure and the crude product was chromatographed using a hexane-ethyl acetate (8:2 v/v) mixture to obtain the title compound. The compound was recrystallized from ethyl acetate solution by slow evaporation.
All H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93–0.98 Å. The Uiso values were set equal to 1.5Ueq of the carrier atom for methyl H atoms and 1.2Ueq for the remaining H atoms. A rotating group model was used for the methyl groups.
Pyranopyrimidine derivatives exhibit antiviral (Shamroukh et al., 2007) and antimicrobial activities (Bedair et al., 2000, 2001; Eid et al., 2004; Abdel Fattah et al., 2004). Previously, we have reported the crystal structures of two pyrano[2,3-d]pyrimidine derivatives (Chinnakali et al., 2007a,b). Now we report here the crystal structure of the title compound.
There are two independent molecules, A and B, in the asymmetric unit, with very similar conformations (Fig. 1). A superposition of the non-H atoms of molecules A and B (Fig. 2) using XP in SHELXTL (Sheldrick, 1998), gave an r.m.s. deviation of 0.437 Å. Molecules A and B differ slightly in the orientation of the ethyl and tosyl groups with respect to the attached pyrrolidine ring, as can be seen from the torsion angles given in Table 1. The geometric parameters in A and B are similar, except for some differences in the C3—C4 [1.552 (4) and 1.539 (3) Å] and C21—C22 [1.494 (4) and 1.518 (3) Å] bond lengths, and C1—N1—C4 [112.5 (2) and 109.5 (2)°] and C3—C4—C21 [117.3 (2) and 111.6 (2)°] bond angles.
In both molecules the pyrrolidine ring adopts an envelope conformation, with the local mirror plane passing through C2 and the midpoint of the bond N1—C4. The relevant asymmetry parameters (Duax et al., 1976) are ΔCs[C2] = 4.3 (2)° for molecule A and 9.6 (2)° for molecule B; Cremer & Pople puckering parameters Q and φ (Cremer & Pople, 1975) are 0.451 (3) Å and 77.2 (3)° for molecule A, and 0.434 (3) Å and 62.7 (3)° for molecule B. In both molecules, the dihydropyran ring also adopts an envelope conformation, with the local mirror plane passing through atoms C2 and C6. The asymmetry parameter ΔCs[C2] is 5.1 (3)° for molecule A and 1.5 (2)° for molecule B; the puckering parameters Q, θ and φ are 0.507 (3) Å, 126.6 (2)° and 294.3 (3)° for molecule A, and 0.524 (3) Å, 126.6 (2)° and 301.6 (3)° for molecule B. The tosyl group is equatorially attached to the pyrrolidine ring in molecule A and in molecule B it is in a biaxial position. The sum of the bond angles around atom N1 of molecule A is 356.7°, indicating sp2 hybridization, whereas in molecule B the corresponding value of 349.2° indicates sp3 hybridization. In both molecules, the sulfonyl group has a distorted tetrahedral geometry (Table 1).
The C1/C3/C4/N1 plane forms dihedral angles of 33.9 (1) and 56.9 (1)°, respectively, with the O3/C5/C3/C7/C6 and C8—C13 planes in molecule A, and 33.2 (1) and 43.1 (1)°, respectively, in molecule B. The dihedral angle between the O3/C5/C3/C7/C6 and C7/C6/N2/C17/N3/C18 planes is 2.6 (1)° in A and 0.7 (1)° in B. The pyrrolidine ring in both molecules is trans-fused to the dihydropyran ring.
Each of the independent molecules exists as a C—H···O hydrogen-bonded dimer, generating a ring of graph-set motif R22(16). The C1A—H1B···O4Bi and C16A—H16C···O4Bi hydrogen bonding interactions (Table 2) form a pair of bifurcated acceptor bonds, generating a ring of graph-set motif R12(7). The above two interactions along with the C1B—H1D···O4Aii interaction link molecules A and B into a chain along the [111] direction. The dimers and the chains are cross-linked into a three-dimensional network by C10B—H10B···O5Aiii and C20B—H20E···O4Av hydrogen bonding interactions, and C—H···π interactions involving the N2B/C6B/C7B/C18B/N3B/C17B ring (centroid Cg1). The geometry of the hydrogen bonds and symmetry codes are given in Table 2. A short H20D···.H22C(-1 + x,1 + y,z) contact of 2.06 Å is observed in the crystal structure.
For related pyranopyrimidine structures, see: Chinnakali et al. (2007a,b). For biological activities of pyranopyrimidine derivatives, see: Abdel Fattah et al. (2004); Bedair et al. (2000, 2001); Eid et al. (2004); Shamroukh et al. (2007). For ring puckering parameters, see: Cremer & Pople (1975). For asymmetry parameters, see: Duax et al. (1976).
Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL (Sheldrick, 1998); molecular graphics: SHELXTL (Sheldrick, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 1998) and PLATON (Spek, 2003).
C22H29N3O5S | Z = 4 |
Mr = 447.55 | F(000) = 952 |
Triclinic, P1 | Dx = 1.367 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.6929 (3) Å | Cell parameters from 5742 reflections |
b = 11.7844 (3) Å | θ = 2.3–29.5° |
c = 17.9339 (4) Å | µ = 0.19 mm−1 |
α = 71.576 (2)° | T = 100 K |
β = 88.034 (2)° | Block, brown |
γ = 68.674 (2)° | 0.35 × 0.26 × 0.23 mm |
V = 2174.87 (10) Å3 |
Bruker SMART APEX2 CCD area-detector diffractometer | 11377 independent reflections |
Radiation source: fine-focus sealed tube | 7677 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
Detector resolution: 8.33 pixels mm-1 | θmax = 29.0°, θmin = 1.2° |
ω scans | h = −15→15 |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −15→16 |
Tmin = 0.937, Tmax = 0.958 | l = −24→24 |
45861 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.166 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0718P)2 + 1.2173P] where P = (Fo2 + 2Fc2)/3 |
11377 reflections | (Δ/σ)max = 0.001 |
571 parameters | Δρmax = 0.65 e Å−3 |
0 restraints | Δρmin = −0.53 e Å−3 |
C22H29N3O5S | γ = 68.674 (2)° |
Mr = 447.55 | V = 2174.87 (10) Å3 |
Triclinic, P1 | Z = 4 |
a = 11.6929 (3) Å | Mo Kα radiation |
b = 11.7844 (3) Å | µ = 0.19 mm−1 |
c = 17.9339 (4) Å | T = 100 K |
α = 71.576 (2)° | 0.35 × 0.26 × 0.23 mm |
β = 88.034 (2)° |
Bruker SMART APEX2 CCD area-detector diffractometer | 11377 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 7677 reflections with I > 2σ(I) |
Tmin = 0.937, Tmax = 0.958 | Rint = 0.073 |
45861 measured reflections |
R[F2 > 2σ(F2)] = 0.065 | 0 restraints |
wR(F2) = 0.166 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.65 e Å−3 |
11377 reflections | Δρmin = −0.53 e Å−3 |
571 parameters |
Experimental. The low-temparture data was collected with the Oxford Cyrosystem Cobra low-temperature attachment. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) 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 | ||
S1A | 0.48868 (6) | −0.06781 (6) | 0.18394 (4) | 0.02654 (16) | |
O1A | 0.56474 (17) | −0.18205 (18) | 0.16642 (11) | 0.0320 (4) | |
O2A | 0.35726 (16) | −0.02178 (19) | 0.16876 (11) | 0.0356 (5) | |
O3A | 0.68594 (14) | 0.23695 (16) | −0.09004 (9) | 0.0242 (4) | |
O4A | 0.38858 (16) | 0.55931 (16) | −0.26961 (10) | 0.0269 (4) | |
O5A | 0.29679 (16) | 0.46092 (17) | −0.01454 (10) | 0.0324 (4) | |
N1A | 0.53278 (19) | 0.0476 (2) | 0.13825 (12) | 0.0283 (5) | |
N2A | 0.53767 (18) | 0.40242 (19) | −0.17589 (11) | 0.0227 (4) | |
N3A | 0.34189 (17) | 0.50835 (18) | −0.14220 (11) | 0.0212 (4) | |
C1A | 0.6604 (2) | 0.0218 (2) | 0.11508 (14) | 0.0245 (5) | |
H1A | 0.7011 | −0.0665 | 0.1159 | 0.029* | |
H1B | 0.7095 | 0.0407 | 0.1485 | 0.029* | |
C2A | 0.6343 (2) | 0.1162 (2) | 0.03180 (13) | 0.0212 (5) | |
H2A | 0.5965 | 0.0835 | −0.0004 | 0.025* | |
C3A | 0.5341 (2) | 0.2365 (2) | 0.04071 (13) | 0.0219 (5) | |
H3A | 0.5706 | 0.2728 | 0.0712 | 0.026* | |
C4A | 0.4443 (2) | 0.1815 (2) | 0.09144 (14) | 0.0264 (5) | |
H4A | 0.3861 | 0.1744 | 0.0568 | 0.032* | |
C5A | 0.7400 (2) | 0.1437 (2) | −0.01069 (13) | 0.0217 (5) | |
C6A | 0.5700 (2) | 0.3222 (2) | −0.09877 (13) | 0.0209 (5) | |
C7A | 0.4910 (2) | 0.3325 (2) | −0.04139 (13) | 0.0212 (5) | |
C8A | 0.5229 (2) | −0.1002 (2) | 0.28523 (14) | 0.0235 (5) | |
C9A | 0.4279 (2) | −0.0639 (2) | 0.33189 (15) | 0.0265 (5) | |
H9A | 0.3466 | −0.0221 | 0.3098 | 0.032* | |
C10A | 0.4554 (2) | −0.0906 (2) | 0.41181 (15) | 0.0267 (5) | |
H10A | 0.3919 | −0.0652 | 0.4428 | 0.032* | |
C11A | 0.5759 (2) | −0.1544 (2) | 0.44643 (14) | 0.0257 (5) | |
C12A | 0.6702 (2) | −0.1893 (2) | 0.39848 (14) | 0.0252 (5) | |
H12A | 0.7515 | −0.2312 | 0.4206 | 0.030* | |
C13A | 0.6447 (2) | −0.1624 (2) | 0.31842 (14) | 0.0238 (5) | |
H13A | 0.7084 | −0.1857 | 0.2871 | 0.029* | |
C14A | 0.6040 (3) | −0.1857 (3) | 0.53346 (15) | 0.0364 (7) | |
H14A | 0.5364 | −0.1313 | 0.5534 | 0.055* | |
H14B | 0.6776 | −0.1715 | 0.5421 | 0.055* | |
H14C | 0.6161 | −0.2743 | 0.5603 | 0.055* | |
C15A | 0.8300 (2) | 0.0273 (2) | −0.02821 (15) | 0.0287 (6) | |
H15A | 0.7862 | −0.0047 | −0.0557 | 0.043* | |
H15B | 0.8707 | −0.0387 | 0.0204 | 0.043* | |
H15C | 0.8901 | 0.0513 | −0.0604 | 0.043* | |
C16A | 0.8046 (2) | 0.2045 (3) | 0.02814 (15) | 0.0289 (6) | |
H16A | 0.7479 | 0.2877 | 0.0275 | 0.043* | |
H16B | 0.8735 | 0.2138 | −0.0003 | 0.043* | |
H16C | 0.8332 | 0.1504 | 0.0817 | 0.043* | |
C17A | 0.4200 (2) | 0.4935 (2) | −0.20027 (13) | 0.0208 (5) | |
C18A | 0.3723 (2) | 0.4348 (2) | −0.06183 (14) | 0.0222 (5) | |
C19A | 0.6236 (2) | 0.3851 (3) | −0.23633 (15) | 0.0331 (6) | |
H19A | 0.7045 | 0.3699 | −0.2158 | 0.050* | |
H19B | 0.5969 | 0.4613 | −0.2819 | 0.050* | |
H19C | 0.6258 | 0.3127 | −0.2509 | 0.050* | |
C20A | 0.2178 (2) | 0.6067 (2) | −0.16769 (15) | 0.0280 (6) | |
H20A | 0.1843 | 0.5975 | −0.2126 | 0.042* | |
H20B | 0.2218 | 0.6908 | −0.1818 | 0.042* | |
H20C | 0.1659 | 0.5964 | −0.1254 | 0.042* | |
C21A | 0.3727 (2) | 0.2528 (3) | 0.14626 (15) | 0.0298 (6) | |
H21A | 0.3189 | 0.3385 | 0.1142 | 0.036* | |
H21B | 0.3207 | 0.2082 | 0.1741 | 0.036* | |
C22A | 0.4492 (3) | 0.2658 (3) | 0.2058 (2) | 0.0517 (9) | |
H22A | 0.3968 | 0.3026 | 0.2412 | 0.078* | |
H22B | 0.4920 | 0.3208 | 0.1793 | 0.078* | |
H22C | 0.5079 | 0.1823 | 0.2351 | 0.078* | |
S1B | −0.01441 (5) | 0.47939 (6) | 0.68320 (3) | 0.02278 (15) | |
O1B | 0.04714 (17) | 0.37022 (16) | 0.65714 (10) | 0.0286 (4) | |
O2B | −0.14485 (15) | 0.54805 (17) | 0.66426 (10) | 0.0282 (4) | |
O3B | 0.17436 (15) | 0.72899 (16) | 0.40075 (9) | 0.0251 (4) | |
O4B | −0.13875 (17) | 1.05506 (17) | 0.23361 (10) | 0.0313 (4) | |
O5B | −0.18272 (15) | 0.97693 (16) | 0.49596 (10) | 0.0269 (4) | |
N1B | 0.05370 (17) | 0.58236 (18) | 0.65284 (11) | 0.0215 (4) | |
N2B | 0.01738 (19) | 0.89330 (19) | 0.32009 (11) | 0.0251 (5) | |
N3B | −0.16202 (18) | 1.01317 (18) | 0.36477 (11) | 0.0217 (4) | |
C1B | 0.1748 (2) | 0.5421 (2) | 0.61971 (13) | 0.0220 (5) | |
H1C | 0.2060 | 0.4511 | 0.6256 | 0.026* | |
H1D | 0.2355 | 0.5608 | 0.6441 | 0.026* | |
C2B | 0.1399 (2) | 0.6257 (2) | 0.53363 (13) | 0.0188 (5) | |
H2B | 0.0877 | 0.5942 | 0.5105 | 0.023* | |
C3B | 0.0581 (2) | 0.7557 (2) | 0.54064 (13) | 0.0192 (5) | |
H3B | 0.1116 | 0.7928 | 0.5570 | 0.023* | |
C4B | −0.0202 (2) | 0.7234 (2) | 0.60906 (13) | 0.0211 (5) | |
H4B | −0.1013 | 0.7341 | 0.5885 | 0.025* | |
C5B | 0.2395 (2) | 0.6380 (2) | 0.47907 (13) | 0.0217 (5) | |
C6B | 0.0629 (2) | 0.8193 (2) | 0.39714 (14) | 0.0219 (5) | |
C7B | −0.0016 (2) | 0.8415 (2) | 0.45937 (13) | 0.0198 (5) | |
C8B | 0.0138 (2) | 0.4238 (2) | 0.78687 (14) | 0.0212 (5) | |
C9B | −0.0840 (2) | 0.4554 (2) | 0.83259 (14) | 0.0239 (5) | |
H9B | −0.1638 | 0.5033 | 0.8088 | 0.029* | |
C10B | −0.0613 (2) | 0.4149 (2) | 0.91380 (14) | 0.0249 (5) | |
H10B | −0.1267 | 0.4362 | 0.9443 | 0.030* | |
C11B | 0.0579 (2) | 0.3427 (2) | 0.95091 (14) | 0.0235 (5) | |
C12B | 0.1548 (2) | 0.3116 (2) | 0.90366 (14) | 0.0223 (5) | |
H12B | 0.2347 | 0.2630 | 0.9273 | 0.027* | |
C13B | 0.1334 (2) | 0.3519 (2) | 0.82234 (14) | 0.0233 (5) | |
H13B | 0.1986 | 0.3312 | 0.7916 | 0.028* | |
C14B | 0.0812 (3) | 0.3002 (3) | 1.03904 (15) | 0.0304 (6) | |
H14D | 0.0449 | 0.2377 | 1.0629 | 0.046* | |
H14F | 0.0452 | 0.3733 | 1.0569 | 0.046* | |
H14E | 0.1684 | 0.2624 | 1.0537 | 0.046* | |
C15B | 0.3098 (2) | 0.5137 (2) | 0.46255 (14) | 0.0266 (5) | |
H15D | 0.3662 | 0.5277 | 0.4237 | 0.040* | |
H15E | 0.2529 | 0.4857 | 0.4431 | 0.040* | |
H15F | 0.3550 | 0.4488 | 0.5104 | 0.040* | |
C16B | 0.3255 (2) | 0.6925 (2) | 0.50306 (16) | 0.0286 (6) | |
H16D | 0.2796 | 0.7789 | 0.5025 | 0.043* | |
H16E | 0.3877 | 0.6931 | 0.4667 | 0.043* | |
H16F | 0.3641 | 0.6401 | 0.5553 | 0.043* | |
C17B | −0.0974 (2) | 0.9910 (2) | 0.30195 (14) | 0.0233 (5) | |
C18B | −0.1188 (2) | 0.9448 (2) | 0.44484 (13) | 0.0209 (5) | |
C19B | 0.0888 (3) | 0.8655 (3) | 0.25440 (14) | 0.0371 (7) | |
H19D | 0.0448 | 0.9268 | 0.2052 | 0.056* | |
H19E | 0.1005 | 0.7801 | 0.2553 | 0.056* | |
H19F | 0.1675 | 0.8716 | 0.2599 | 0.056* | |
C20B | −0.2844 (2) | 1.1152 (2) | 0.34687 (15) | 0.0286 (6) | |
H20D | −0.3280 | 1.1097 | 0.3045 | 0.043* | |
H20E | −0.2765 | 1.1975 | 0.3315 | 0.043* | |
H20F | −0.3292 | 1.1053 | 0.3928 | 0.043* | |
C21B | −0.0342 (2) | 0.8060 (2) | 0.66169 (13) | 0.0230 (5) | |
H21C | 0.0471 | 0.7899 | 0.6835 | 0.028* | |
H21D | −0.0695 | 0.8960 | 0.6293 | 0.028* | |
C22B | −0.1138 (2) | 0.7828 (2) | 0.72915 (15) | 0.0302 (6) | |
H22D | −0.1927 | 0.7921 | 0.7087 | 0.045* | |
H22E | −0.1249 | 0.8444 | 0.7559 | 0.045* | |
H22F | −0.0743 | 0.6973 | 0.7655 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1A | 0.0270 (3) | 0.0263 (3) | 0.0237 (3) | −0.0093 (3) | 0.0002 (2) | −0.0053 (3) |
O1A | 0.0379 (10) | 0.0300 (10) | 0.0316 (10) | −0.0135 (9) | 0.0048 (8) | −0.0138 (8) |
O2A | 0.0280 (10) | 0.0426 (12) | 0.0328 (10) | −0.0134 (9) | −0.0022 (8) | −0.0070 (9) |
O3A | 0.0218 (8) | 0.0204 (9) | 0.0191 (8) | 0.0009 (7) | −0.0006 (6) | −0.0017 (7) |
O4A | 0.0324 (10) | 0.0213 (9) | 0.0202 (9) | −0.0063 (7) | −0.0052 (7) | −0.0013 (7) |
O5A | 0.0324 (10) | 0.0242 (10) | 0.0248 (9) | 0.0032 (8) | 0.0055 (7) | −0.0038 (8) |
N1A | 0.0223 (10) | 0.0217 (11) | 0.0278 (11) | −0.0018 (9) | 0.0002 (8) | 0.0018 (9) |
N2A | 0.0245 (10) | 0.0180 (10) | 0.0186 (10) | −0.0023 (8) | −0.0003 (8) | −0.0032 (8) |
N3A | 0.0220 (10) | 0.0141 (9) | 0.0209 (10) | −0.0018 (8) | −0.0018 (8) | −0.0023 (8) |
C1A | 0.0225 (12) | 0.0193 (12) | 0.0233 (12) | −0.0026 (10) | −0.0008 (9) | −0.0014 (10) |
C2A | 0.0212 (11) | 0.0156 (11) | 0.0215 (12) | −0.0032 (9) | −0.0028 (9) | −0.0028 (9) |
C3A | 0.0250 (12) | 0.0170 (11) | 0.0179 (11) | −0.0023 (9) | −0.0018 (9) | −0.0042 (9) |
C4A | 0.0258 (12) | 0.0226 (13) | 0.0215 (12) | −0.0034 (10) | −0.0043 (9) | −0.0007 (10) |
C5A | 0.0229 (12) | 0.0175 (11) | 0.0173 (11) | −0.0039 (9) | −0.0047 (9) | 0.0007 (9) |
C6A | 0.0219 (11) | 0.0160 (11) | 0.0204 (11) | −0.0031 (9) | −0.0024 (9) | −0.0043 (9) |
C7A | 0.0235 (12) | 0.0155 (11) | 0.0193 (11) | −0.0025 (9) | −0.0025 (9) | −0.0038 (9) |
C8A | 0.0283 (13) | 0.0164 (11) | 0.0241 (12) | −0.0090 (10) | 0.0030 (9) | −0.0037 (10) |
C9A | 0.0269 (13) | 0.0173 (12) | 0.0319 (14) | −0.0073 (10) | 0.0032 (10) | −0.0045 (10) |
C10A | 0.0318 (13) | 0.0150 (11) | 0.0310 (14) | −0.0076 (10) | 0.0091 (10) | −0.0063 (10) |
C11A | 0.0352 (14) | 0.0143 (11) | 0.0267 (13) | −0.0081 (10) | 0.0036 (10) | −0.0071 (10) |
C12A | 0.0284 (13) | 0.0152 (11) | 0.0284 (13) | −0.0054 (10) | −0.0005 (10) | −0.0050 (10) |
C13A | 0.0260 (12) | 0.0159 (11) | 0.0273 (13) | −0.0061 (10) | 0.0043 (10) | −0.0064 (10) |
C14A | 0.0501 (17) | 0.0266 (14) | 0.0269 (14) | −0.0072 (13) | 0.0023 (12) | −0.0094 (12) |
C15A | 0.0233 (12) | 0.0246 (13) | 0.0271 (13) | 0.0005 (10) | 0.0002 (10) | −0.0048 (11) |
C16A | 0.0302 (13) | 0.0251 (13) | 0.0273 (13) | −0.0115 (11) | −0.0041 (10) | −0.0013 (11) |
C17A | 0.0257 (12) | 0.0139 (11) | 0.0206 (12) | −0.0053 (9) | −0.0030 (9) | −0.0047 (9) |
C18A | 0.0262 (12) | 0.0137 (11) | 0.0216 (12) | −0.0028 (9) | −0.0018 (9) | −0.0038 (9) |
C19A | 0.0309 (14) | 0.0327 (15) | 0.0213 (13) | −0.0013 (12) | 0.0054 (10) | −0.0027 (11) |
C20A | 0.0272 (13) | 0.0178 (12) | 0.0264 (13) | 0.0013 (10) | −0.0033 (10) | −0.0013 (10) |
C21A | 0.0314 (14) | 0.0270 (14) | 0.0244 (13) | −0.0061 (11) | 0.0020 (10) | −0.0054 (11) |
C22A | 0.0455 (19) | 0.057 (2) | 0.061 (2) | −0.0115 (16) | −0.0033 (15) | −0.0380 (18) |
S1B | 0.0253 (3) | 0.0189 (3) | 0.0208 (3) | −0.0067 (2) | −0.0011 (2) | −0.0036 (2) |
O1B | 0.0377 (10) | 0.0221 (9) | 0.0284 (9) | −0.0124 (8) | 0.0025 (8) | −0.0097 (8) |
O2B | 0.0248 (9) | 0.0265 (10) | 0.0291 (10) | −0.0091 (8) | −0.0032 (7) | −0.0036 (8) |
O3B | 0.0262 (9) | 0.0185 (8) | 0.0197 (8) | 0.0009 (7) | 0.0021 (7) | −0.0027 (7) |
O4B | 0.0396 (11) | 0.0227 (9) | 0.0205 (9) | −0.0025 (8) | −0.0090 (7) | −0.0021 (7) |
O5B | 0.0276 (9) | 0.0199 (9) | 0.0241 (9) | −0.0003 (7) | 0.0023 (7) | −0.0053 (7) |
N1B | 0.0212 (10) | 0.0139 (9) | 0.0207 (10) | −0.0017 (8) | −0.0003 (7) | 0.0002 (8) |
N2B | 0.0311 (11) | 0.0188 (10) | 0.0164 (10) | −0.0012 (9) | −0.0002 (8) | −0.0031 (8) |
N3B | 0.0238 (10) | 0.0141 (9) | 0.0207 (10) | −0.0023 (8) | −0.0034 (8) | −0.0020 (8) |
C1B | 0.0212 (11) | 0.0164 (11) | 0.0219 (12) | −0.0024 (9) | 0.0004 (9) | −0.0029 (9) |
C2B | 0.0181 (11) | 0.0141 (11) | 0.0199 (11) | −0.0022 (9) | −0.0013 (8) | −0.0040 (9) |
C3B | 0.0218 (11) | 0.0142 (11) | 0.0172 (11) | −0.0027 (9) | −0.0005 (8) | −0.0037 (9) |
C4B | 0.0240 (12) | 0.0125 (11) | 0.0188 (11) | −0.0015 (9) | −0.0016 (9) | −0.0002 (9) |
C5B | 0.0231 (12) | 0.0141 (11) | 0.0189 (11) | 0.0003 (9) | −0.0039 (9) | −0.0014 (9) |
C6B | 0.0245 (12) | 0.0157 (11) | 0.0205 (12) | −0.0037 (9) | −0.0011 (9) | −0.0035 (9) |
C7B | 0.0232 (11) | 0.0133 (11) | 0.0190 (11) | −0.0035 (9) | −0.0030 (9) | −0.0035 (9) |
C8B | 0.0270 (12) | 0.0118 (11) | 0.0210 (12) | −0.0057 (9) | −0.0002 (9) | −0.0018 (9) |
C9B | 0.0233 (12) | 0.0163 (11) | 0.0262 (13) | −0.0053 (10) | 0.0006 (9) | −0.0014 (10) |
C10B | 0.0290 (13) | 0.0168 (12) | 0.0271 (13) | −0.0078 (10) | 0.0077 (10) | −0.0060 (10) |
C11B | 0.0296 (13) | 0.0170 (11) | 0.0234 (12) | −0.0084 (10) | 0.0024 (10) | −0.0064 (10) |
C12B | 0.0234 (12) | 0.0167 (11) | 0.0232 (12) | −0.0049 (9) | −0.0003 (9) | −0.0046 (10) |
C13B | 0.0263 (12) | 0.0168 (12) | 0.0225 (12) | −0.0050 (10) | 0.0042 (9) | −0.0044 (10) |
C14B | 0.0385 (15) | 0.0261 (14) | 0.0254 (13) | −0.0106 (12) | 0.0036 (11) | −0.0085 (11) |
C15B | 0.0262 (12) | 0.0208 (12) | 0.0255 (13) | −0.0010 (10) | 0.0018 (10) | −0.0070 (10) |
C16B | 0.0273 (13) | 0.0230 (13) | 0.0336 (14) | −0.0093 (11) | 0.0034 (10) | −0.0066 (11) |
C17B | 0.0287 (13) | 0.0175 (12) | 0.0216 (12) | −0.0063 (10) | −0.0034 (9) | −0.0057 (10) |
C18B | 0.0230 (12) | 0.0141 (11) | 0.0213 (12) | −0.0041 (9) | −0.0021 (9) | −0.0028 (9) |
C19B | 0.0424 (16) | 0.0354 (16) | 0.0170 (12) | 0.0008 (13) | 0.0038 (11) | −0.0049 (11) |
C20B | 0.0254 (13) | 0.0211 (13) | 0.0264 (13) | 0.0015 (10) | −0.0071 (10) | −0.0017 (10) |
C21B | 0.0288 (12) | 0.0161 (11) | 0.0184 (11) | −0.0040 (10) | −0.0010 (9) | −0.0030 (9) |
C22B | 0.0373 (15) | 0.0241 (13) | 0.0251 (13) | −0.0061 (11) | 0.0062 (11) | −0.0091 (11) |
S1A—O2A | 1.4349 (19) | S1B—O2B | 1.4356 (17) |
S1A—O1A | 1.4421 (18) | S1B—O1B | 1.4405 (17) |
S1A—N1A | 1.602 (2) | S1B—N1B | 1.630 (2) |
S1A—C8A | 1.762 (2) | S1B—C8B | 1.763 (2) |
O3A—C6A | 1.340 (3) | O3B—C6B | 1.337 (3) |
O3A—C5A | 1.483 (3) | O3B—C5B | 1.493 (3) |
O4A—C17A | 1.224 (3) | O4B—C17B | 1.223 (3) |
O5A—C18A | 1.229 (3) | O5B—C18B | 1.229 (3) |
N1A—C1A | 1.483 (3) | N1B—C1B | 1.488 (3) |
N1A—C4A | 1.516 (3) | N1B—C4B | 1.518 (3) |
N2A—C6A | 1.378 (3) | N2B—C17B | 1.379 (3) |
N2A—C17A | 1.381 (3) | N2B—C6B | 1.380 (3) |
N2A—C19A | 1.464 (3) | N2B—C19B | 1.473 (3) |
N3A—C17A | 1.372 (3) | N3B—C17B | 1.376 (3) |
N3A—C18A | 1.406 (3) | N3B—C18B | 1.410 (3) |
N3A—C20A | 1.465 (3) | N3B—C20B | 1.460 (3) |
C1A—C2A | 1.515 (3) | C1B—C2B | 1.520 (3) |
C1A—H1A | 0.97 | C1B—H1C | 0.97 |
C1A—H1B | 0.97 | C1B—H1D | 0.97 |
C2A—C5A | 1.511 (3) | C2B—C5B | 1.513 (3) |
C2A—C3A | 1.526 (3) | C2B—C3B | 1.525 (3) |
C2A—H2A | 0.98 | C2B—H2B | 0.98 |
C3A—C7A | 1.512 (3) | C3B—C7B | 1.503 (3) |
C3A—C4A | 1.552 (4) | C3B—C4B | 1.539 (3) |
C3A—H3A | 0.98 | C3B—H3B | 0.98 |
C4A—C21A | 1.526 (3) | C4B—C21B | 1.523 (3) |
C4A—H4A | 0.98 | C4B—H4B | 0.98 |
C5A—C15A | 1.513 (3) | C5B—C16B | 1.512 (4) |
C5A—C16A | 1.521 (3) | C5B—C15B | 1.513 (3) |
C6A—C7A | 1.363 (3) | C6B—C7B | 1.366 (3) |
C7A—C18A | 1.433 (3) | C7B—C18B | 1.428 (3) |
C8A—C9A | 1.391 (3) | C8B—C9B | 1.391 (3) |
C8A—C13A | 1.394 (3) | C8B—C13B | 1.392 (3) |
C9A—C10A | 1.389 (3) | C9B—C10B | 1.384 (3) |
C9A—H9A | 0.93 | C9B—H9B | 0.93 |
C10A—C11A | 1.389 (3) | C10B—C11B | 1.397 (3) |
C10A—H10A | 0.93 | C10B—H10B | 0.93 |
C11A—C12A | 1.398 (3) | C11B—C12B | 1.402 (3) |
C11A—C14A | 1.504 (3) | C11B—C14B | 1.501 (3) |
C12A—C13A | 1.387 (3) | C12B—C13B | 1.384 (3) |
C12A—H12A | 0.93 | C12B—H12B | 0.93 |
C13A—H13A | 0.93 | C13B—H13B | 0.93 |
C14A—H14A | 0.96 | C14B—H14D | 0.96 |
C14A—H14B | 0.96 | C14B—H14F | 0.96 |
C14A—H14C | 0.96 | C14B—H14E | 0.96 |
C15A—H15A | 0.96 | C15B—H15D | 0.96 |
C15A—H15B | 0.96 | C15B—H15E | 0.96 |
C15A—H15C | 0.96 | C15B—H15F | 0.96 |
C16A—H16A | 0.96 | C16B—H16D | 0.96 |
C16A—H16B | 0.96 | C16B—H16E | 0.96 |
C16A—H16C | 0.96 | C16B—H16F | 0.96 |
C19A—H19A | 0.96 | C19B—H19D | 0.96 |
C19A—H19B | 0.96 | C19B—H19E | 0.96 |
C19A—H19C | 0.96 | C19B—H19F | 0.96 |
C20A—H20A | 0.96 | C20B—H20D | 0.96 |
C20A—H20B | 0.96 | C20B—H20E | 0.96 |
C20A—H20C | 0.96 | C20B—H20F | 0.96 |
C21A—C22A | 1.494 (4) | C21B—C22B | 1.518 (3) |
C21A—H21A | 0.97 | C21B—H21C | 0.97 |
C21A—H21B | 0.97 | C21B—H21D | 0.97 |
C22A—H22A | 0.96 | C22B—H22D | 0.96 |
C22A—H22B | 0.96 | C22B—H22E | 0.96 |
C22A—H22C | 0.96 | C22B—H22F | 0.96 |
O2A—S1A—O1A | 119.32 (12) | O2B—S1B—O1B | 119.55 (11) |
O2A—S1A—N1A | 107.97 (11) | O2B—S1B—N1B | 108.35 (10) |
O1A—S1A—N1A | 108.82 (11) | O1B—S1B—N1B | 109.20 (11) |
O2A—S1A—C8A | 107.96 (11) | O2B—S1B—C8B | 107.46 (11) |
O1A—S1A—C8A | 106.09 (11) | O1B—S1B—C8B | 106.77 (11) |
N1A—S1A—C8A | 105.92 (12) | N1B—S1B—C8B | 104.49 (11) |
C6A—O3A—C5A | 119.34 (17) | C6B—O3B—C5B | 119.78 (17) |
C1A—N1A—C4A | 112.5 (2) | C1B—N1B—C4B | 109.53 (18) |
C1A—N1A—S1A | 121.13 (16) | C1B—N1B—S1B | 118.94 (15) |
C4A—N1A—S1A | 123.19 (17) | C4B—N1B—S1B | 120.74 (16) |
C6A—N2A—C17A | 121.34 (19) | C17B—N2B—C6B | 121.58 (19) |
C6A—N2A—C19A | 120.77 (19) | C17B—N2B—C19B | 118.04 (19) |
C17A—N2A—C19A | 117.62 (19) | C6B—N2B—C19B | 120.32 (19) |
C17A—N3A—C18A | 124.64 (19) | C17B—N3B—C18B | 124.85 (19) |
C17A—N3A—C20A | 116.39 (19) | C17B—N3B—C20B | 117.32 (19) |
C18A—N3A—C20A | 118.95 (19) | C18B—N3B—C20B | 117.83 (19) |
N1A—C1A—C2A | 100.01 (18) | N1B—C1B—C2B | 100.96 (17) |
N1A—C1A—H1A | 111.8 | N1B—C1B—H1C | 111.6 |
C2A—C1A—H1A | 111.8 | C2B—C1B—H1C | 111.6 |
N1A—C1A—H1B | 111.8 | N1B—C1B—H1D | 111.6 |
C2A—C1A—H1B | 111.8 | C2B—C1B—H1D | 111.6 |
H1A—C1A—H1B | 109.5 | H1C—C1B—H1D | 109.4 |
C5A—C2A—C1A | 119.02 (19) | C5B—C2B—C1B | 120.04 (18) |
C5A—C2A—C3A | 112.9 (2) | C5B—C2B—C3B | 111.6 (2) |
C1A—C2A—C3A | 102.73 (18) | C1B—C2B—C3B | 101.85 (17) |
C5A—C2A—H2A | 107.2 | C5B—C2B—H2B | 107.6 |
C1A—C2A—H2A | 107.2 | C1B—C2B—H2B | 107.6 |
C3A—C2A—H2A | 107.2 | C3B—C2B—H2B | 107.6 |
C7A—C3A—C2A | 106.90 (18) | C7B—C3B—C2B | 107.04 (17) |
C7A—C3A—C4A | 120.5 (2) | C7B—C3B—C4B | 120.97 (19) |
C2A—C3A—C4A | 102.81 (19) | C2B—C3B—C4B | 104.91 (18) |
C7A—C3A—H3A | 108.7 | C7B—C3B—H3B | 107.8 |
C2A—C3A—H3A | 108.7 | C2B—C3B—H3B | 107.8 |
C4A—C3A—H3A | 108.7 | C4B—C3B—H3B | 107.8 |
N1A—C4A—C21A | 110.93 (19) | N1B—C4B—C21B | 111.43 (18) |
N1A—C4A—C3A | 100.64 (18) | N1B—C4B—C3B | 102.66 (17) |
C21A—C4A—C3A | 117.3 (2) | C21B—C4B—C3B | 111.6 (2) |
N1A—C4A—H4A | 109.2 | N1B—C4B—H4B | 110.3 |
C21A—C4A—H4A | 109.2 | C21B—C4B—H4B | 110.3 |
C3A—C4A—H4A | 109.2 | C3B—C4B—H4B | 110.3 |
O3A—C5A—C2A | 106.18 (17) | O3B—C5B—C16B | 107.2 (2) |
O3A—C5A—C15A | 103.56 (18) | O3B—C5B—C2B | 106.21 (17) |
C2A—C5A—C15A | 112.1 (2) | C16B—C5B—C2B | 115.17 (19) |
O3A—C5A—C16A | 107.48 (19) | O3B—C5B—C15B | 103.75 (18) |
C2A—C5A—C16A | 114.5 (2) | C16B—C5B—C15B | 111.6 (2) |
C15A—C5A—C16A | 112.1 (2) | C2B—C5B—C15B | 112.0 (2) |
O3A—C6A—C7A | 126.8 (2) | O3B—C6B—C7B | 126.8 (2) |
O3A—C6A—N2A | 110.75 (19) | O3B—C6B—N2B | 111.38 (19) |
C7A—C6A—N2A | 122.5 (2) | C7B—C6B—N2B | 121.8 (2) |
C6A—C7A—C18A | 118.3 (2) | C6B—C7B—C18B | 119.4 (2) |
C6A—C7A—C3A | 118.2 (2) | C6B—C7B—C3B | 117.01 (19) |
C18A—C7A—C3A | 123.5 (2) | C18B—C7B—C3B | 123.5 (2) |
C9A—C8A—C13A | 120.2 (2) | C9B—C8B—C13B | 120.4 (2) |
C9A—C8A—S1A | 119.74 (19) | C9B—C8B—S1B | 119.44 (18) |
C13A—C8A—S1A | 120.07 (18) | C13B—C8B—S1B | 120.09 (18) |
C10A—C9A—C8A | 119.5 (2) | C10B—C9B—C8B | 119.4 (2) |
C10A—C9A—H9A | 120.3 | C10B—C9B—H9B | 120.3 |
C8A—C9A—H9A | 120.3 | C8B—C9B—H9B | 120.3 |
C9A—C10A—C11A | 121.3 (2) | C9B—C10B—C11B | 121.3 (2) |
C9A—C10A—H10A | 119.3 | C9B—C10B—H10B | 119.3 |
C11A—C10A—H10A | 119.3 | C11B—C10B—H10B | 119.3 |
C10A—C11A—C12A | 118.4 (2) | C10B—C11B—C12B | 118.3 (2) |
C10A—C11A—C14A | 120.8 (2) | C10B—C11B—C14B | 120.7 (2) |
C12A—C11A—C14A | 120.8 (2) | C12B—C11B—C14B | 121.0 (2) |
C13A—C12A—C11A | 121.1 (2) | C13B—C12B—C11B | 121.0 (2) |
C13A—C12A—H12A | 119.4 | C13B—C12B—H12B | 119.5 |
C11A—C12A—H12A | 119.4 | C11B—C12B—H12B | 119.5 |
C12A—C13A—C8A | 119.5 (2) | C12B—C13B—C8B | 119.6 (2) |
C12A—C13A—H13A | 120.2 | C12B—C13B—H13B | 120.2 |
C8A—C13A—H13A | 120.2 | C8B—C13B—H13B | 120.2 |
C11A—C14A—H14A | 109.5 | C11B—C14B—H14D | 109.5 |
C11A—C14A—H14B | 109.5 | C11B—C14B—H14F | 109.5 |
H14A—C14A—H14B | 109.5 | H14D—C14B—H14F | 109.5 |
C11A—C14A—H14C | 109.5 | C11B—C14B—H14E | 109.5 |
H14A—C14A—H14C | 109.5 | H14D—C14B—H14E | 109.5 |
H14B—C14A—H14C | 109.5 | H14F—C14B—H14E | 109.5 |
C5A—C15A—H15A | 109.5 | C5B—C15B—H15D | 109.5 |
C5A—C15A—H15B | 109.5 | C5B—C15B—H15E | 109.5 |
H15A—C15A—H15B | 109.5 | H15D—C15B—H15E | 109.5 |
C5A—C15A—H15C | 109.5 | C5B—C15B—H15F | 109.5 |
H15A—C15A—H15C | 109.5 | H15D—C15B—H15F | 109.5 |
H15B—C15A—H15C | 109.5 | H15E—C15B—H15F | 109.5 |
C5A—C16A—H16A | 109.5 | C5B—C16B—H16D | 109.5 |
C5A—C16A—H16B | 109.5 | C5B—C16B—H16E | 109.5 |
H16A—C16A—H16B | 109.5 | H16D—C16B—H16E | 109.5 |
C5A—C16A—H16C | 109.5 | C5B—C16B—H16F | 109.5 |
H16A—C16A—H16C | 109.5 | H16D—C16B—H16F | 109.5 |
H16B—C16A—H16C | 109.5 | H16E—C16B—H16F | 109.5 |
O4A—C17A—N3A | 122.1 (2) | O4B—C17B—N3B | 122.0 (2) |
O4A—C17A—N2A | 121.6 (2) | O4B—C17B—N2B | 121.6 (2) |
N3A—C17A—N2A | 116.27 (19) | N3B—C17B—N2B | 116.4 (2) |
O5A—C18A—N3A | 118.9 (2) | O5B—C18B—N3B | 119.0 (2) |
O5A—C18A—C7A | 124.7 (2) | O5B—C18B—C7B | 125.2 (2) |
N3A—C18A—C7A | 116.5 (2) | N3B—C18B—C7B | 115.8 (2) |
N2A—C19A—H19A | 109.5 | N2B—C19B—H19D | 109.5 |
N2A—C19A—H19B | 109.5 | N2B—C19B—H19E | 109.5 |
H19A—C19A—H19B | 109.5 | H19D—C19B—H19E | 109.5 |
N2A—C19A—H19C | 109.5 | N2B—C19B—H19F | 109.5 |
H19A—C19A—H19C | 109.5 | H19D—C19B—H19F | 109.5 |
H19B—C19A—H19C | 109.5 | H19E—C19B—H19F | 109.5 |
N3A—C20A—H20A | 109.5 | N3B—C20B—H20D | 109.5 |
N3A—C20A—H20B | 109.5 | N3B—C20B—H20E | 109.5 |
H20A—C20A—H20B | 109.5 | H20D—C20B—H20E | 109.5 |
N3A—C20A—H20C | 109.5 | N3B—C20B—H20F | 109.5 |
H20A—C20A—H20C | 109.5 | H20D—C20B—H20F | 109.5 |
H20B—C20A—H20C | 109.5 | H20E—C20B—H20F | 109.5 |
C22A—C21A—C4A | 115.6 (2) | C22B—C21B—C4B | 114.8 (2) |
C22A—C21A—H21A | 108.4 | C22B—C21B—H21C | 108.6 |
C4A—C21A—H21A | 108.4 | C4B—C21B—H21C | 108.6 |
C22A—C21A—H21B | 108.4 | C22B—C21B—H21D | 108.6 |
C4A—C21A—H21B | 108.4 | C4B—C21B—H21D | 108.6 |
H21A—C21A—H21B | 107.4 | H21C—C21B—H21D | 107.5 |
C21A—C22A—H22A | 109.5 | C21B—C22B—H22D | 109.5 |
C21A—C22A—H22B | 109.5 | C21B—C22B—H22E | 109.5 |
H22A—C22A—H22B | 109.5 | H22D—C22B—H22E | 109.5 |
C21A—C22A—H22C | 109.5 | C21B—C22B—H22F | 109.5 |
H22A—C22A—H22C | 109.5 | H22D—C22B—H22F | 109.5 |
H22B—C22A—H22C | 109.5 | H22E—C22B—H22F | 109.5 |
O2A—S1A—N1A—C1A | −155.63 (19) | O2B—S1B—N1B—C1B | −143.30 (16) |
O1A—S1A—N1A—C1A | −24.8 (2) | O1B—S1B—N1B—C1B | −11.57 (19) |
C8A—S1A—N1A—C1A | 88.9 (2) | C8B—S1B—N1B—C1B | 102.36 (17) |
O2A—S1A—N1A—C4A | 2.6 (2) | O2B—S1B—N1B—C4B | −2.67 (19) |
O1A—S1A—N1A—C4A | 133.44 (19) | O1B—S1B—N1B—C4B | 129.07 (17) |
C8A—S1A—N1A—C4A | −112.9 (2) | C8B—S1B—N1B—C4B | −117.01 (17) |
C4A—N1A—C1A—C2A | −24.3 (3) | C4B—N1B—C1B—C2B | −32.8 (2) |
S1A—N1A—C1A—C2A | 136.04 (18) | S1B—N1B—C1B—C2B | 111.85 (18) |
N1A—C1A—C2A—C5A | 167.8 (2) | N1B—C1B—C2B—C5B | 167.6 (2) |
N1A—C1A—C2A—C3A | 42.2 (2) | N1B—C1B—C2B—C3B | 43.9 (2) |
C5A—C2A—C3A—C7A | 56.8 (3) | C5B—C2B—C3B—C7B | 61.0 (2) |
C1A—C2A—C3A—C7A | −173.7 (2) | C1B—C2B—C3B—C7B | −169.79 (19) |
C5A—C2A—C3A—C4A | −175.30 (18) | C5B—C2B—C3B—C4B | −169.37 (18) |
C1A—C2A—C3A—C4A | −45.8 (2) | C1B—C2B—C3B—C4B | −40.1 (2) |
C1A—N1A—C4A—C21A | −127.9 (2) | C1B—N1B—C4B—C21B | −111.4 (2) |
S1A—N1A—C4A—C21A | 72.2 (3) | S1B—N1B—C4B—C21B | 104.7 (2) |
C1A—N1A—C4A—C3A | −3.1 (3) | C1B—N1B—C4B—C3B | 8.3 (2) |
S1A—N1A—C4A—C3A | −162.95 (17) | S1B—N1B—C4B—C3B | −135.65 (17) |
C7A—C3A—C4A—N1A | 148.0 (2) | C7B—C3B—C4B—N1B | 140.7 (2) |
C2A—C3A—C4A—N1A | 29.3 (2) | C2B—C3B—C4B—N1B | 19.8 (2) |
C7A—C3A—C4A—C21A | −91.7 (3) | C7B—C3B—C4B—C21B | −99.9 (2) |
C2A—C3A—C4A—C21A | 149.6 (2) | C2B—C3B—C4B—C21B | 139.25 (19) |
C6A—O3A—C5A—C2A | 31.6 (3) | C6B—O3B—C5B—C16B | −95.6 (2) |
C6A—O3A—C5A—C15A | 149.7 (2) | C6B—O3B—C5B—C2B | 28.0 (3) |
C6A—O3A—C5A—C16A | −91.4 (2) | C6B—O3B—C5B—C15B | 146.2 (2) |
C1A—C2A—C5A—O3A | 179.20 (19) | C1B—C2B—C5B—O3B | −178.26 (19) |
C3A—C2A—C5A—O3A | −60.2 (2) | C3B—C2B—C5B—O3B | −59.3 (2) |
C1A—C2A—C5A—C15A | 66.8 (3) | C1B—C2B—C5B—C16B | −59.8 (3) |
C3A—C2A—C5A—C15A | −172.64 (19) | C3B—C2B—C5B—C16B | 59.1 (3) |
C1A—C2A—C5A—C16A | −62.4 (3) | C1B—C2B—C5B—C15B | 69.1 (3) |
C3A—C2A—C5A—C16A | 58.2 (3) | C3B—C2B—C5B—C15B | −171.96 (19) |
C5A—O3A—C6A—C7A | −1.6 (4) | C5B—O3B—C6B—C7B | 1.2 (4) |
C5A—O3A—C6A—N2A | 178.30 (19) | C5B—O3B—C6B—N2B | −179.6 (2) |
C17A—N2A—C6A—O3A | 176.2 (2) | C17B—N2B—C6B—O3B | 178.7 (2) |
C19A—N2A—C6A—O3A | 2.4 (3) | C19B—N2B—C6B—O3B | 1.5 (3) |
C17A—N2A—C6A—C7A | −4.0 (4) | C17B—N2B—C6B—C7B | −2.0 (4) |
C19A—N2A—C6A—C7A | −177.7 (2) | C19B—N2B—C6B—C7B | −179.2 (2) |
O3A—C6A—C7A—C18A | 176.8 (2) | O3B—C6B—C7B—C18B | 178.4 (2) |
N2A—C6A—C7A—C18A | −3.0 (4) | N2B—C6B—C7B—C18B | −0.8 (4) |
O3A—C6A—C7A—C3A | −2.3 (4) | O3B—C6B—C7B—C3B | 0.0 (4) |
N2A—C6A—C7A—C3A | 177.9 (2) | N2B—C6B—C7B—C3B | −179.2 (2) |
C2A—C3A—C7A—C6A | −24.4 (3) | C2B—C3B—C7B—C6B | −29.9 (3) |
C4A—C3A—C7A—C6A | −141.0 (2) | C4B—C3B—C7B—C6B | −149.7 (2) |
C2A—C3A—C7A—C18A | 156.5 (2) | C2B—C3B—C7B—C18B | 151.8 (2) |
C4A—C3A—C7A—C18A | 39.9 (3) | C4B—C3B—C7B—C18B | 31.9 (3) |
O2A—S1A—C8A—C9A | −8.3 (2) | O2B—S1B—C8B—C9B | −2.6 (2) |
O1A—S1A—C8A—C9A | −137.3 (2) | O1B—S1B—C8B—C9B | −132.0 (2) |
N1A—S1A—C8A—C9A | 107.1 (2) | N1B—S1B—C8B—C9B | 112.4 (2) |
O2A—S1A—C8A—C13A | 171.4 (2) | O2B—S1B—C8B—C13B | 179.20 (19) |
O1A—S1A—C8A—C13A | 42.5 (2) | O1B—S1B—C8B—C13B | 49.8 (2) |
N1A—S1A—C8A—C13A | −73.1 (2) | N1B—S1B—C8B—C13B | −65.8 (2) |
C13A—C8A—C9A—C10A | −0.2 (4) | C13B—C8B—C9B—C10B | 0.1 (4) |
S1A—C8A—C9A—C10A | 179.52 (19) | S1B—C8B—C9B—C10B | −178.11 (19) |
C8A—C9A—C10A—C11A | −0.9 (4) | C8B—C9B—C10B—C11B | −0.1 (4) |
C9A—C10A—C11A—C12A | 1.3 (4) | C9B—C10B—C11B—C12B | −0.2 (4) |
C9A—C10A—C11A—C14A | −178.4 (2) | C9B—C10B—C11B—C14B | 179.6 (2) |
C10A—C11A—C12A—C13A | −0.7 (4) | C10B—C11B—C12B—C13B | 0.5 (4) |
C14A—C11A—C12A—C13A | 179.0 (2) | C14B—C11B—C12B—C13B | −179.3 (2) |
C11A—C12A—C13A—C8A | −0.3 (4) | C11B—C12B—C13B—C8B | −0.5 (4) |
C9A—C8A—C13A—C12A | 0.8 (4) | C9B—C8B—C13B—C12B | 0.2 (4) |
S1A—C8A—C13A—C12A | −178.93 (19) | S1B—C8B—C13B—C12B | 178.37 (18) |
C18A—N3A—C17A—O4A | 179.3 (2) | C18B—N3B—C17B—O4B | −178.6 (2) |
C20A—N3A—C17A—O4A | 0.7 (3) | C20B—N3B—C17B—O4B | 1.4 (4) |
C18A—N3A—C17A—N2A | −2.6 (3) | C18B—N3B—C17B—N2B | 0.7 (4) |
C20A—N3A—C17A—N2A | 178.8 (2) | C20B—N3B—C17B—N2B | −179.3 (2) |
C6A—N2A—C17A—O4A | −175.3 (2) | C6B—N2B—C17B—O4B | −178.7 (2) |
C19A—N2A—C17A—O4A | −1.3 (3) | C19B—N2B—C17B—O4B | −1.4 (4) |
C6A—N2A—C17A—N3A | 6.6 (3) | C6B—N2B—C17B—N3B | 2.0 (3) |
C19A—N2A—C17A—N3A | −179.4 (2) | C19B—N2B—C17B—N3B | 179.3 (2) |
C17A—N3A—C18A—O5A | 176.6 (2) | C17B—N3B—C18B—O5B | 176.9 (2) |
C20A—N3A—C18A—O5A | −4.8 (3) | C20B—N3B—C18B—O5B | −3.1 (3) |
C17A—N3A—C18A—C7A | −4.0 (3) | C17B—N3B—C18B—C7B | −3.3 (3) |
C20A—N3A—C18A—C7A | 174.6 (2) | C20B—N3B—C18B—C7B | 176.7 (2) |
C6A—C7A—C18A—O5A | −173.9 (2) | C6B—C7B—C18B—O5B | −177.0 (2) |
C3A—C7A—C18A—O5A | 5.2 (4) | C3B—C7B—C18B—O5B | 1.3 (4) |
C6A—C7A—C18A—N3A | 6.7 (3) | C6B—C7B—C18B—N3B | 3.2 (3) |
C3A—C7A—C18A—N3A | −174.2 (2) | C3B—C7B—C18B—N3B | −178.5 (2) |
N1A—C4A—C21A—C22A | 56.7 (3) | N1B—C4B—C21B—C22B | −67.7 (3) |
C3A—C4A—C21A—C22A | −58.1 (3) | C3B—C4B—C21B—C22B | 178.11 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1A—H1B···O4Bi | 0.97 | 2.46 | 3.424 (3) | 171 |
C1B—H1C···O1B | 0.97 | 2.36 | 2.838 (3) | 110 |
C1B—H1D···O4Aii | 0.97 | 2.40 | 3.346 (3) | 166 |
C10B—H10B···O5Aiii | 0.93 | 2.46 | 3.374 (3) | 168 |
C15A—H15A···O2Aiv | 0.96 | 2.54 | 3.426 (3) | 153 |
C15B—H15E···O2Biii | 0.96 | 2.55 | 3.434 (3) | 154 |
C16A—H16C···O4Bi | 0.96 | 2.58 | 3.512 (3) | 164 |
C20B—H20E···O4Av | 0.96 | 2.55 | 3.387 (3) | 145 |
C21A—H21A···O5A | 0.97 | 2.27 | 3.040 (3) | 136 |
C21B—H21D···O5B | 0.97 | 2.50 | 3.152 (3) | 125 |
C21B—H21D···Cg1vi | 0.97 | 2.96 | 3.591 (3) | 123 |
Symmetry codes: (i) x+1, y−1, z; (ii) x, y, z+1; (iii) −x, −y+1, −z+1; (iv) −x+1, −y, −z; (v) −x, −y+2, −z; (vi) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C22H29N3O5S |
Mr | 447.55 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 11.6929 (3), 11.7844 (3), 17.9339 (4) |
α, β, γ (°) | 71.576 (2), 88.034 (2), 68.674 (2) |
V (Å3) | 2174.87 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.19 |
Crystal size (mm) | 0.35 × 0.26 × 0.23 |
Data collection | |
Diffractometer | Bruker SMART APEX2 CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.937, 0.958 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 45861, 11377, 7677 |
Rint | 0.073 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.166, 1.02 |
No. of reflections | 11377 |
No. of parameters | 571 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.65, −0.53 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 1998) and PLATON (Spek, 2003).
O2A—S1A—O1A | 119.32 (12) | O2B—S1B—O1B | 119.55 (11) |
N1A—S1A—C8A | 105.92 (12) | N1B—S1B—C8B | 104.49 (11) |
O1A—S1A—N1A—C1A | −24.8 (2) | O1B—S1B—N1B—C1B | −11.57 (19) |
C8A—S1A—N1A—C1A | 88.9 (2) | C8B—S1B—N1B—C1B | 102.36 (17) |
N1A—S1A—C8A—C9A | 107.1 (2) | N1B—S1B—C8B—C9B | 112.4 (2) |
N1A—C4A—C21A—C22A | 56.7 (3) | N1B—C4B—C21B—C22B | −67.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1A—H1B···O4Bi | 0.97 | 2.46 | 3.424 (3) | 171 |
C1B—H1C···O1B | 0.97 | 2.36 | 2.838 (3) | 110 |
C1B—H1D···O4Aii | 0.97 | 2.40 | 3.346 (3) | 166 |
C10B—H10B···O5Aiii | 0.93 | 2.46 | 3.374 (3) | 168 |
C15A—H15A···O2Aiv | 0.96 | 2.54 | 3.426 (3) | 153 |
C15B—H15E···O2Biii | 0.96 | 2.55 | 3.434 (3) | 154 |
C16A—H16C···O4Bi | 0.96 | 2.58 | 3.512 (3) | 164 |
C20B—H20E···O4Av | 0.96 | 2.55 | 3.387 (3) | 145 |
C21A—H21A···O5A | 0.97 | 2.27 | 3.040 (3) | 136 |
C21B—H21D···O5B | 0.97 | 2.50 | 3.152 (3) | 125 |
C21B—H21D···Cg1vi | 0.97 | 2.96 | 3.591 (3) | 123 |
Symmetry codes: (i) x+1, y−1, z; (ii) x, y, z+1; (iii) −x, −y+1, −z+1; (iv) −x+1, −y, −z; (v) −x, −y+2, −z; (vi) −x, −y+2, −z+1. |
Pyranopyrimidine derivatives exhibit antiviral (Shamroukh et al., 2007) and antimicrobial activities (Bedair et al., 2000, 2001; Eid et al., 2004; Abdel Fattah et al., 2004). Previously, we have reported the crystal structures of two pyrano[2,3-d]pyrimidine derivatives (Chinnakali et al., 2007a,b). Now we report here the crystal structure of the title compound.
There are two independent molecules, A and B, in the asymmetric unit, with very similar conformations (Fig. 1). A superposition of the non-H atoms of molecules A and B (Fig. 2) using XP in SHELXTL (Sheldrick, 1998), gave an r.m.s. deviation of 0.437 Å. Molecules A and B differ slightly in the orientation of the ethyl and tosyl groups with respect to the attached pyrrolidine ring, as can be seen from the torsion angles given in Table 1. The geometric parameters in A and B are similar, except for some differences in the C3—C4 [1.552 (4) and 1.539 (3) Å] and C21—C22 [1.494 (4) and 1.518 (3) Å] bond lengths, and C1—N1—C4 [112.5 (2) and 109.5 (2)°] and C3—C4—C21 [117.3 (2) and 111.6 (2)°] bond angles.
In both molecules the pyrrolidine ring adopts an envelope conformation, with the local mirror plane passing through C2 and the midpoint of the bond N1—C4. The relevant asymmetry parameters (Duax et al., 1976) are ΔCs[C2] = 4.3 (2)° for molecule A and 9.6 (2)° for molecule B; Cremer & Pople puckering parameters Q and φ (Cremer & Pople, 1975) are 0.451 (3) Å and 77.2 (3)° for molecule A, and 0.434 (3) Å and 62.7 (3)° for molecule B. In both molecules, the dihydropyran ring also adopts an envelope conformation, with the local mirror plane passing through atoms C2 and C6. The asymmetry parameter ΔCs[C2] is 5.1 (3)° for molecule A and 1.5 (2)° for molecule B; the puckering parameters Q, θ and φ are 0.507 (3) Å, 126.6 (2)° and 294.3 (3)° for molecule A, and 0.524 (3) Å, 126.6 (2)° and 301.6 (3)° for molecule B. The tosyl group is equatorially attached to the pyrrolidine ring in molecule A and in molecule B it is in a biaxial position. The sum of the bond angles around atom N1 of molecule A is 356.7°, indicating sp2 hybridization, whereas in molecule B the corresponding value of 349.2° indicates sp3 hybridization. In both molecules, the sulfonyl group has a distorted tetrahedral geometry (Table 1).
The C1/C3/C4/N1 plane forms dihedral angles of 33.9 (1) and 56.9 (1)°, respectively, with the O3/C5/C3/C7/C6 and C8—C13 planes in molecule A, and 33.2 (1) and 43.1 (1)°, respectively, in molecule B. The dihedral angle between the O3/C5/C3/C7/C6 and C7/C6/N2/C17/N3/C18 planes is 2.6 (1)° in A and 0.7 (1)° in B. The pyrrolidine ring in both molecules is trans-fused to the dihydropyran ring.
Each of the independent molecules exists as a C—H···O hydrogen-bonded dimer, generating a ring of graph-set motif R22(16). The C1A—H1B···O4Bi and C16A—H16C···O4Bi hydrogen bonding interactions (Table 2) form a pair of bifurcated acceptor bonds, generating a ring of graph-set motif R12(7). The above two interactions along with the C1B—H1D···O4Aii interaction link molecules A and B into a chain along the [111] direction. The dimers and the chains are cross-linked into a three-dimensional network by C10B—H10B···O5Aiii and C20B—H20E···O4Av hydrogen bonding interactions, and C—H···π interactions involving the N2B/C6B/C7B/C18B/N3B/C17B ring (centroid Cg1). The geometry of the hydrogen bonds and symmetry codes are given in Table 2. A short H20D···.H22C(-1 + x,1 + y,z) contact of 2.06 Å is observed in the crystal structure.