Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103022649/bm1543sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103022649/bm1543Isup2.hkl |
CCDC reference: 226139
Crystalline CEX was obtained by suspending small amounts of technical grade CEX powder in a saturated aqueous solution and allowing slow evaporation to take place at room temperature. The crystals were isolated from solution, blotted free of liquid, packed in well sealed containers, with a minimum of void space, and stored at 277 K in a refrigirator to maintain their stochiometry for the purpose of analysis. Thermogravimetric analysis showed the presence of 9.0% (w/w) water (cf. 9.4% required for CEX·2H2O) and microanalytical data also suggested the presence of approximately two water molecules. Exposure to ambient laboratory conditions led to rapid loss of water (giving CEX·H2O). Samples were transported to the SRS in sealed containers packed with dry ice. Prior to data collection, they were exposed to a humidity of more than 75% for 2 h to ensure maximum hydration.
Disorder in one molecule of CEX was modelled using isotropic C atoms split over two sites with a total occupancy of 1. The H atoms of the water molecules could not be positioned reliably and were omitted from the final model. All other H atoms were placed in idealized positions and refined in riding mode (methyl and NH3 H orientations were obtained by refining a torsion angle, and were given Uiso values of 1.5Ueq of the parent atom; for other H atoms, Uiso(H) was 1.2Ueq [N—H = 0.91 Å (NH3), N—H = 0.88 Å (NH), C—H = 0.98 Å (CH3), C—H = 0.99 (CH2), C—H = 1.00 (CH)Å and C—H = 0.95 Å (sp2CH). The absolute configuration could not be determined from the intensity data and is therefore based on the known geometry of cephalosporins (Kemperman et al., 1999).
Data collection: SMART (Bruker, 1995); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1974); software used to prepare material for publication: SHELXL97.
C16H17N3O4S·1.9H2O | F(000) = 2414 |
Mr = 381.88 | Dx = 1.404 Mg m−3 |
Monoclinic, C2 | Synchrotron radiation, λ = 0.6891 Å |
a = 31.548 (2) Å | Cell parameters from 14822 reflections |
b = 11.8574 (9) Å | θ = 2.1–27.5° |
c = 15.6654 (11) Å | µ = 0.22 mm−1 |
β = 112.364 (2)° | T = 150 K |
V = 5419.3 (7) Å3 | Needle, colourless |
Z = 12 | 0.20 × 0.05 × 0.01 mm |
Bruker AXS SMART CCD diffractometer | 10703 independent reflections |
Radiation source: Daresbury SRS Station 9.8 | 8136 reflections with I > 2σ(I) |
Si 111 monochromator | Rint = 0.047 |
Detector resolution: 8.192 pixels mm-1 | θmax = 26.0°, θmin = 2.1° |
ω rotation with narrow frames scans | h = −21→40 |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | k = −14→15 |
Tmin = 0.96, Tmax = 1.00 | l = −19→19 |
14822 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)] = 0.074 | H-atom parameters constrained |
wR(F2) = 0.193 | w = 1/[σ2(Fo2) + (0.1215P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
10703 reflections | Δρmax = 0.58 e Å−3 |
717 parameters | Δρmin = −0.47 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.21 (10) |
C16H17N3O4S·1.9H2O | V = 5419.3 (7) Å3 |
Mr = 381.88 | Z = 12 |
Monoclinic, C2 | Synchrotron radiation, λ = 0.6891 Å |
a = 31.548 (2) Å | µ = 0.22 mm−1 |
b = 11.8574 (9) Å | T = 150 K |
c = 15.6654 (11) Å | 0.20 × 0.05 × 0.01 mm |
β = 112.364 (2)° |
Bruker AXS SMART CCD diffractometer | 10703 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 8136 reflections with I > 2σ(I) |
Tmin = 0.96, Tmax = 1.00 | Rint = 0.047 |
14822 measured reflections |
R[F2 > 2σ(F2)] = 0.074 | H-atom parameters constrained |
wR(F2) = 0.193 | Δρmax = 0.58 e Å−3 |
S = 1.01 | Δρmin = −0.47 e Å−3 |
10703 reflections | Absolute structure: Flack (1983) |
717 parameters | Absolute structure parameter: 0.21 (10) |
1 restraint |
Experimental. Bruker's SAINT software was used to integrate the data. As this is a synchrotron experiment the main effect is incident beam decay. The correction for this is bundled with the small effects for absorption and sample decay. The diffrn_standards_decay_% entry is thus large as it is mainly due to decay of the incident beam. |
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 | Occ. (<1) | |
S1 | 0.30860 (4) | 0.01130 (11) | 0.40610 (8) | 0.0236 (3) | |
O1 | 0.19989 (14) | −0.3407 (4) | 0.2921 (3) | 0.0390 (10) | |
O2 | 0.23321 (12) | −0.3796 (3) | 0.4426 (2) | 0.0301 (8) | |
O3 | 0.16511 (11) | −0.1020 (3) | 0.3409 (2) | 0.0261 (8) | |
O4 | 0.19007 (12) | 0.2541 (3) | 0.2256 (2) | 0.0298 (8) | |
N1 | 0.23724 (13) | −0.1280 (4) | 0.3328 (3) | 0.0212 (8) | |
N2 | 0.21788 (14) | 0.1343 (4) | 0.3462 (3) | 0.0228 (9) | |
H2 | 0.2267 | 0.1275 | 0.4064 | 0.027* | |
N3 | 0.19169 (14) | 0.4254 (4) | 0.3497 (3) | 0.0266 (9) | |
H3A | 0.2025 | 0.4867 | 0.3865 | 0.040* | |
H3B | 0.1658 | 0.4000 | 0.3559 | 0.040* | |
H3C | 0.1852 | 0.4449 | 0.2899 | 0.040* | |
C1 | 0.33549 (16) | −0.1257 (4) | 0.4209 (3) | 0.0223 (10) | |
H1A | 0.3468 | −0.1369 | 0.3706 | 0.027* | |
H1B | 0.3625 | −0.1254 | 0.4798 | 0.027* | |
C2 | 0.30577 (16) | −0.2263 (4) | 0.4216 (3) | 0.0182 (9) | |
C3 | 0.26017 (15) | −0.2251 (4) | 0.3810 (3) | 0.0177 (9) | |
C4 | 0.25885 (16) | −0.0312 (4) | 0.3079 (3) | 0.0223 (10) | |
H4 | 0.2651 | −0.0429 | 0.2505 | 0.027* | |
C5 | 0.21423 (16) | 0.0355 (4) | 0.2917 (3) | 0.0199 (10) | |
H5 | 0.1964 | 0.0501 | 0.2247 | 0.024* | |
C6 | 0.19767 (16) | −0.0737 (4) | 0.3254 (3) | 0.0211 (10) | |
C7 | 0.33213 (18) | −0.3275 (5) | 0.4670 (4) | 0.0308 (12) | |
H7A | 0.3111 | −0.3907 | 0.4600 | 0.046* | |
H7B | 0.3489 | −0.3119 | 0.5327 | 0.046* | |
H7C | 0.3539 | −0.3468 | 0.4383 | 0.046* | |
C8 | 0.22826 (16) | −0.3217 (4) | 0.3714 (3) | 0.0224 (10) | |
C9 | 0.20835 (16) | 0.2367 (4) | 0.3085 (3) | 0.0231 (10) | |
C10 | 0.22680 (16) | 0.3353 (4) | 0.3772 (3) | 0.0227 (10) | |
H10 | 0.2320 | 0.3090 | 0.4410 | 0.027* | |
C11 | 0.27147 (16) | 0.3723 (4) | 0.3730 (3) | 0.0245 (10) | |
C12 | 0.31180 (19) | 0.3494 (5) | 0.4463 (4) | 0.0365 (13) | |
H12 | 0.3109 | 0.3124 | 0.4994 | 0.044* | |
C13 | 0.35360 (19) | 0.3796 (6) | 0.4434 (5) | 0.0454 (16) | |
H13 | 0.3813 | 0.3633 | 0.4940 | 0.054* | |
C14 | 0.3548 (2) | 0.4344 (6) | 0.3654 (5) | 0.0437 (16) | |
H14 | 0.3832 | 0.4573 | 0.3633 | 0.052* | |
C15 | 0.3152 (2) | 0.4547 (6) | 0.2927 (4) | 0.0403 (14) | |
H15 | 0.3161 | 0.4894 | 0.2388 | 0.048* | |
C16 | 0.27354 (19) | 0.4255 (5) | 0.2961 (4) | 0.0293 (11) | |
H16 | 0.2460 | 0.4421 | 0.2451 | 0.035* | |
S2 | 0.03365 (4) | 0.94752 (12) | 0.34163 (9) | 0.0296 (3) | |
O5 | 0.11181 (12) | 1.3454 (3) | 0.3529 (2) | 0.0256 (8) | |
O6 | 0.06821 (16) | 1.3330 (3) | 0.2033 (3) | 0.0381 (10) | |
O7 | 0.11226 (11) | 1.0941 (3) | 0.1899 (2) | 0.0234 (7) | |
O8 | 0.02084 (12) | 0.7409 (3) | 0.1037 (2) | 0.0285 (8) | |
N4 | 0.05036 (13) | 1.1100 (3) | 0.2383 (3) | 0.0192 (8) | |
N5 | 0.07413 (13) | 0.8519 (3) | 0.2084 (3) | 0.0208 (8) | |
H5A | 0.1009 | 0.8546 | 0.2547 | 0.025* | |
N6 | 0.07344 (15) | 0.5556 (4) | 0.1525 (3) | 0.0263 (9) | |
H6A | 0.0753 | 0.4887 | 0.1821 | 0.039* | |
H6B | 0.0937 | 0.5559 | 0.1239 | 0.039* | |
H6C | 0.0445 | 0.5649 | 0.1097 | 0.039* | |
C17 | 0.02042 (19) | 1.0766 (5) | 0.3875 (4) | 0.0305 (12) | |
H17A | −0.0132 | 1.0879 | 0.3600 | 0.037* | |
H17B | 0.0292 | 1.0669 | 0.4548 | 0.037* | |
C18 | 0.04298 (16) | 1.1819 (5) | 0.3720 (3) | 0.0279 (11) | |
C19 | 0.05790 (15) | 1.1967 (4) | 0.3033 (3) | 0.0193 (9) | |
C20 | 0.04900 (15) | 0.9538 (4) | 0.1746 (3) | 0.0183 (9) | |
H20 | 0.0298 | 0.9492 | 0.1071 | 0.022* | |
C21 | 0.02259 (15) | 1.0082 (4) | 0.2292 (3) | 0.0201 (9) | |
H21 | −0.0107 | 1.0198 | 0.1916 | 0.024* | |
C22 | 0.07791 (16) | 1.0618 (4) | 0.1990 (3) | 0.0192 (10) | |
C23 | 0.04504 (18) | 1.2751 (5) | 0.4392 (4) | 0.0332 (13) | |
H23A | 0.0579 | 1.3432 | 0.4230 | 0.050* | |
H23B | 0.0645 | 1.2514 | 0.5019 | 0.050* | |
H23C | 0.0141 | 1.2912 | 0.4364 | 0.050* | |
C24 | 0.08137 (16) | 1.3010 (4) | 0.2851 (3) | 0.0209 (10) | |
C25 | 0.05692 (16) | 0.7514 (4) | 0.1697 (3) | 0.0194 (9) | |
C26 | 0.08443 (16) | 0.6491 (4) | 0.2203 (3) | 0.0215 (10) | |
H26 | 0.1180 | 0.6662 | 0.2441 | 0.026* | |
C27 | 0.06980 (17) | 0.6227 (4) | 0.3003 (3) | 0.0235 (10) | |
C28 | 0.10077 (18) | 0.6407 (5) | 0.3891 (4) | 0.0308 (12) | |
H28 | 0.1313 | 0.6626 | 0.3997 | 0.037* | |
C29 | 0.0872 (2) | 0.6267 (6) | 0.4630 (4) | 0.0366 (13) | |
H29 | 0.1080 | 0.6419 | 0.5242 | 0.044* | |
C30 | 0.0434 (2) | 0.5905 (7) | 0.4470 (4) | 0.0467 (17) | |
H30 | 0.0344 | 0.5780 | 0.4977 | 0.056* | |
C31 | 0.0120 (2) | 0.5721 (7) | 0.3578 (5) | 0.0504 (17) | |
H31 | −0.0184 | 0.5491 | 0.3474 | 0.060* | |
C32 | 0.02550 (19) | 0.5876 (5) | 0.2843 (4) | 0.0326 (12) | |
H32 | 0.0045 | 0.5743 | 0.2230 | 0.039* | |
S3 | 0.38897 (8) | 0.35790 (15) | 0.18246 (13) | 0.0574 (5) | |
O9 | 0.3285 (3) | −0.0229 (5) | 0.0085 (5) | 0.085 (2) | |
O10 | 0.3989 (3) | −0.0226 (5) | 0.0104 (6) | 0.094 (2) | |
O11 | 0.37462 (15) | 0.2227 (4) | −0.0865 (3) | 0.0417 (10) | |
O12 | 0.45530 (12) | 0.5732 (3) | 0.0199 (2) | 0.0241 (7) | |
N7 | 0.40532 (19) | 0.2020 (4) | 0.0744 (4) | 0.0387 (12) | |
N8 | 0.39530 (14) | 0.4642 (4) | 0.0118 (3) | 0.0246 (9) | |
H8 | 0.3656 | 0.4629 | −0.0014 | 0.030* | |
N9 | 0.39751 (17) | 0.7552 (4) | −0.0509 (3) | 0.0310 (10) | |
H9A | 0.4280 | 0.7511 | −0.0391 | 0.047* | |
H9B | 0.3909 | 0.8240 | −0.0334 | 0.047* | |
H9C | 0.3813 | 0.7453 | −0.1124 | 0.047* | |
C33 | 0.3774 (4) | 0.2175 (9) | 0.2268 (8) | 0.035 (3)* | 0.58 (2) |
H33A | 0.4053 | 0.1959 | 0.2803 | 0.042* | 0.58 (2) |
H33B | 0.3526 | 0.2288 | 0.2501 | 0.042* | 0.58 (2) |
C34 | 0.3641 (5) | 0.1190 (10) | 0.1606 (10) | 0.040 (3)* | 0.58 (2) |
C35 | 0.3831 (3) | 0.1136 (5) | 0.1007 (6) | 0.057 (2) | |
C36 | 0.4257 (2) | 0.3037 (5) | 0.1282 (4) | 0.0367 (13) | |
H36 | 0.4583 | 0.2933 | 0.1717 | 0.044* | |
C37 | 0.42095 (18) | 0.3599 (5) | 0.0363 (4) | 0.0275 (11) | |
H37 | 0.4512 | 0.3660 | 0.0297 | 0.033* | |
C38 | 0.39532 (19) | 0.2533 (5) | −0.0092 (4) | 0.0292 (12) | |
C39 | 0.3428 (5) | 0.0277 (11) | 0.1970 (9) | 0.044 (3)* | 0.58 (2) |
H39A | 0.3507 | −0.0459 | 0.1787 | 0.066* | 0.58 (2) |
H39B | 0.3094 | 0.0370 | 0.1715 | 0.066* | 0.58 (2) |
H39C | 0.3544 | 0.0324 | 0.2644 | 0.066* | 0.58 (2) |
C40 | 0.3694 (4) | 0.0133 (7) | 0.0344 (7) | 0.073 (3) | |
C41 | 0.41541 (17) | 0.5627 (4) | 0.0085 (3) | 0.0221 (10) | |
C42 | 0.38497 (18) | 0.6656 (4) | 0.0017 (3) | 0.0239 (10) | |
H42 | 0.3520 | 0.6445 | −0.0312 | 0.029* | |
C43 | 0.39311 (17) | 0.7045 (4) | 0.0996 (3) | 0.0252 (11) | |
C44 | 0.3612 (2) | 0.6805 (5) | 0.1375 (4) | 0.0355 (13) | |
H44 | 0.3338 | 0.6411 | 0.1028 | 0.043* | |
C45 | 0.3697 (3) | 0.7153 (6) | 0.2279 (5) | 0.0464 (16) | |
H45 | 0.3479 | 0.7004 | 0.2549 | 0.056* | |
C46 | 0.4090 (2) | 0.7702 (6) | 0.2768 (4) | 0.0450 (17) | |
H46 | 0.4150 | 0.7906 | 0.3390 | 0.054* | |
C47 | 0.4405 (2) | 0.7975 (7) | 0.2390 (4) | 0.0504 (18) | |
H47 | 0.4670 | 0.8404 | 0.2730 | 0.060* | |
C48 | 0.43266 (18) | 0.7610 (6) | 0.1501 (4) | 0.0372 (14) | |
H48 | 0.4549 | 0.7752 | 0.1241 | 0.045* | |
C100 | 0.3646 (8) | 0.0353 (16) | 0.2328 (15) | 0.053 (5)* | 0.42 (2) |
C101 | 0.3825 (5) | 0.1304 (10) | 0.1922 (9) | 0.018 (3)* | 0.42 (2) |
C102 | 0.3993 (6) | 0.2337 (14) | 0.2559 (11) | 0.035 (4)* | 0.42 (2) |
O13 | 0.29840 (15) | 0.4602 (5) | −0.0604 (3) | 0.0522 (12) | |
O14 | 0.23811 (19) | 0.7581 (5) | 0.1559 (4) | 0.050 (2) | 0.860 (15) |
O15 | 0.1647 (2) | 0.5017 (5) | 0.1667 (4) | 0.043 (2) | 0.716 (18) |
O16 | 0.2499 (2) | 0.6052 (7) | 0.0212 (4) | 0.063 (3) | 0.793 (15) |
O21 | 0.2440 (8) | 0.475 (2) | 0.0549 (17) | 0.058 (9)* | 0.207 (15) |
O22 | 0.2516 (8) | 0.667 (2) | 0.1584 (17) | 0.027 (9)* | 0.140 (15) |
O17 | 0.0119 (2) | 0.2744 (6) | 0.0345 (4) | 0.0251 (15)* | 0.50 |
O18 | 0.2201 (3) | 0.2776 (8) | 0.0743 (6) | 0.063 (3)* | 0.67 (2) |
O19 | 0.4856 (3) | −0.0100 (8) | 0.0342 (6) | 0.047 (2)* | 0.50 |
O20 | 0.2498 (8) | 0.236 (2) | 0.1159 (16) | 0.089 (9)* | 0.33 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0202 (5) | 0.0229 (6) | 0.0279 (6) | −0.0049 (5) | 0.0092 (5) | −0.0042 (5) |
O1 | 0.041 (2) | 0.032 (2) | 0.035 (2) | −0.0101 (18) | 0.0039 (18) | −0.0117 (18) |
O2 | 0.036 (2) | 0.025 (2) | 0.0324 (19) | −0.0045 (16) | 0.0164 (16) | 0.0032 (16) |
O3 | 0.0230 (17) | 0.0230 (19) | 0.0338 (19) | −0.0037 (14) | 0.0125 (15) | −0.0001 (15) |
O4 | 0.038 (2) | 0.021 (2) | 0.0270 (19) | −0.0086 (15) | 0.0080 (16) | 0.0035 (15) |
N1 | 0.0215 (19) | 0.026 (2) | 0.0155 (18) | −0.0044 (17) | 0.0057 (15) | 0.0022 (16) |
N2 | 0.029 (2) | 0.020 (2) | 0.020 (2) | −0.0002 (17) | 0.0097 (17) | 0.0039 (16) |
N3 | 0.025 (2) | 0.018 (2) | 0.041 (2) | 0.0006 (16) | 0.0178 (19) | 0.0045 (18) |
C1 | 0.020 (2) | 0.024 (3) | 0.022 (2) | −0.0020 (19) | 0.0067 (18) | −0.002 (2) |
C2 | 0.025 (2) | 0.021 (3) | 0.010 (2) | −0.0033 (18) | 0.0079 (17) | −0.0026 (18) |
C3 | 0.020 (2) | 0.013 (2) | 0.021 (2) | 0.0005 (17) | 0.0090 (18) | −0.0010 (18) |
C4 | 0.025 (2) | 0.025 (3) | 0.014 (2) | −0.0037 (19) | 0.0033 (18) | 0.0016 (19) |
C5 | 0.028 (2) | 0.020 (3) | 0.012 (2) | −0.0032 (19) | 0.0084 (18) | 0.0036 (17) |
C6 | 0.022 (2) | 0.022 (3) | 0.016 (2) | −0.0037 (19) | 0.0028 (18) | −0.0001 (18) |
C7 | 0.027 (3) | 0.025 (3) | 0.039 (3) | −0.001 (2) | 0.012 (2) | −0.002 (2) |
C8 | 0.027 (2) | 0.015 (2) | 0.030 (3) | 0.002 (2) | 0.015 (2) | 0.002 (2) |
C9 | 0.022 (2) | 0.023 (3) | 0.028 (3) | −0.007 (2) | 0.014 (2) | −0.003 (2) |
C10 | 0.026 (2) | 0.024 (3) | 0.019 (2) | −0.003 (2) | 0.0096 (19) | 0.000 (2) |
C11 | 0.027 (2) | 0.020 (3) | 0.030 (3) | −0.003 (2) | 0.015 (2) | −0.008 (2) |
C12 | 0.036 (3) | 0.032 (3) | 0.036 (3) | −0.003 (2) | 0.008 (2) | −0.011 (3) |
C13 | 0.025 (3) | 0.043 (4) | 0.061 (4) | 0.004 (3) | 0.007 (3) | −0.017 (3) |
C14 | 0.035 (3) | 0.038 (4) | 0.071 (4) | −0.010 (3) | 0.035 (3) | −0.023 (3) |
C15 | 0.047 (3) | 0.037 (3) | 0.052 (4) | −0.007 (3) | 0.036 (3) | −0.013 (3) |
C16 | 0.037 (3) | 0.026 (3) | 0.026 (3) | −0.001 (2) | 0.013 (2) | −0.004 (2) |
S2 | 0.0338 (7) | 0.0290 (8) | 0.0293 (7) | −0.0066 (6) | 0.0156 (5) | 0.0074 (6) |
O5 | 0.0277 (18) | 0.025 (2) | 0.0245 (17) | −0.0069 (14) | 0.0109 (14) | −0.0064 (15) |
O6 | 0.063 (3) | 0.016 (2) | 0.030 (2) | −0.0086 (18) | 0.0128 (19) | 0.0013 (16) |
O7 | 0.0220 (17) | 0.0199 (19) | 0.0287 (18) | −0.0027 (14) | 0.0102 (14) | 0.0024 (14) |
O8 | 0.036 (2) | 0.0179 (19) | 0.0247 (18) | −0.0006 (15) | 0.0038 (15) | 0.0047 (15) |
N4 | 0.024 (2) | 0.011 (2) | 0.0195 (19) | −0.0053 (15) | 0.0048 (16) | 0.0008 (15) |
N5 | 0.022 (2) | 0.013 (2) | 0.023 (2) | −0.0015 (16) | 0.0048 (16) | −0.0007 (17) |
N6 | 0.032 (2) | 0.014 (2) | 0.040 (2) | −0.0017 (17) | 0.022 (2) | 0.0018 (18) |
C17 | 0.037 (3) | 0.039 (3) | 0.026 (3) | −0.006 (2) | 0.023 (2) | −0.001 (2) |
C18 | 0.022 (2) | 0.040 (3) | 0.019 (2) | −0.002 (2) | 0.0058 (19) | −0.002 (2) |
C19 | 0.022 (2) | 0.021 (3) | 0.015 (2) | −0.0031 (19) | 0.0081 (18) | −0.0032 (18) |
C20 | 0.026 (2) | 0.011 (2) | 0.020 (2) | −0.0035 (18) | 0.0113 (18) | −0.0023 (18) |
C21 | 0.022 (2) | 0.019 (2) | 0.021 (2) | −0.004 (2) | 0.0096 (18) | 0.002 (2) |
C22 | 0.029 (3) | 0.010 (2) | 0.016 (2) | 0.0014 (18) | 0.0056 (19) | 0.0018 (17) |
C23 | 0.025 (3) | 0.049 (4) | 0.025 (3) | −0.004 (2) | 0.009 (2) | −0.009 (2) |
C24 | 0.028 (2) | 0.015 (2) | 0.021 (2) | 0.0036 (19) | 0.0108 (19) | −0.0039 (19) |
C25 | 0.026 (2) | 0.016 (2) | 0.018 (2) | −0.0041 (19) | 0.0096 (19) | −0.0036 (18) |
C26 | 0.023 (2) | 0.016 (2) | 0.028 (2) | −0.0036 (18) | 0.013 (2) | 0.003 (2) |
C27 | 0.029 (2) | 0.014 (2) | 0.030 (3) | 0.0018 (19) | 0.015 (2) | 0.004 (2) |
C28 | 0.029 (3) | 0.031 (3) | 0.035 (3) | 0.003 (2) | 0.015 (2) | 0.003 (2) |
C29 | 0.042 (3) | 0.049 (4) | 0.019 (2) | 0.010 (3) | 0.011 (2) | 0.000 (2) |
C30 | 0.054 (4) | 0.064 (5) | 0.032 (3) | 0.007 (3) | 0.028 (3) | 0.010 (3) |
C31 | 0.041 (3) | 0.061 (5) | 0.056 (4) | −0.006 (3) | 0.026 (3) | 0.009 (4) |
C32 | 0.037 (3) | 0.035 (3) | 0.025 (3) | 0.001 (2) | 0.011 (2) | 0.002 (2) |
S3 | 0.1130 (16) | 0.0310 (9) | 0.0562 (10) | 0.0305 (10) | 0.0636 (11) | 0.0138 (8) |
O9 | 0.111 (5) | 0.060 (4) | 0.116 (5) | −0.016 (4) | 0.078 (4) | 0.008 (4) |
O10 | 0.128 (5) | 0.027 (3) | 0.172 (7) | 0.002 (3) | 0.108 (6) | −0.010 (4) |
O11 | 0.053 (2) | 0.024 (2) | 0.060 (3) | −0.0029 (19) | 0.035 (2) | −0.007 (2) |
O12 | 0.0315 (19) | 0.0180 (18) | 0.0278 (18) | 0.0012 (14) | 0.0168 (15) | −0.0006 (14) |
N7 | 0.064 (3) | 0.017 (2) | 0.058 (3) | 0.010 (2) | 0.048 (3) | 0.010 (2) |
N8 | 0.028 (2) | 0.023 (2) | 0.028 (2) | 0.0052 (18) | 0.0168 (17) | 0.0029 (18) |
N9 | 0.059 (3) | 0.016 (2) | 0.022 (2) | 0.007 (2) | 0.020 (2) | −0.0041 (18) |
C35 | 0.095 (5) | 0.020 (3) | 0.094 (5) | 0.022 (3) | 0.079 (5) | 0.022 (3) |
C36 | 0.058 (4) | 0.025 (3) | 0.037 (3) | 0.011 (3) | 0.028 (3) | 0.007 (2) |
C37 | 0.033 (3) | 0.026 (3) | 0.031 (3) | 0.002 (2) | 0.020 (2) | 0.005 (2) |
C38 | 0.039 (3) | 0.022 (3) | 0.041 (3) | 0.000 (2) | 0.031 (3) | −0.006 (2) |
C40 | 0.122 (7) | 0.035 (4) | 0.108 (7) | 0.011 (5) | 0.097 (6) | 0.017 (5) |
C41 | 0.033 (3) | 0.023 (3) | 0.014 (2) | 0.002 (2) | 0.013 (2) | 0.0000 (19) |
C42 | 0.034 (3) | 0.018 (3) | 0.021 (2) | 0.009 (2) | 0.011 (2) | −0.0017 (19) |
C43 | 0.033 (3) | 0.023 (3) | 0.020 (2) | 0.008 (2) | 0.010 (2) | −0.001 (2) |
C44 | 0.043 (3) | 0.033 (3) | 0.039 (3) | 0.000 (3) | 0.026 (3) | −0.004 (3) |
C45 | 0.068 (4) | 0.041 (4) | 0.047 (4) | 0.003 (3) | 0.040 (3) | 0.003 (3) |
C46 | 0.055 (4) | 0.059 (5) | 0.017 (3) | 0.019 (3) | 0.009 (3) | −0.005 (3) |
C47 | 0.036 (3) | 0.071 (5) | 0.031 (3) | 0.012 (3) | −0.003 (3) | −0.025 (3) |
C48 | 0.026 (3) | 0.060 (4) | 0.026 (3) | 0.000 (3) | 0.010 (2) | −0.019 (3) |
O13 | 0.045 (2) | 0.056 (3) | 0.057 (3) | −0.002 (2) | 0.021 (2) | 0.006 (2) |
O14 | 0.058 (3) | 0.054 (4) | 0.041 (3) | −0.006 (3) | 0.023 (3) | −0.008 (3) |
O15 | 0.056 (4) | 0.025 (3) | 0.036 (3) | 0.009 (3) | 0.005 (3) | 0.006 (3) |
O16 | 0.061 (4) | 0.076 (5) | 0.061 (4) | −0.012 (4) | 0.032 (3) | −0.018 (4) |
S1—C4 | 1.802 (5) | C23—H23A | 0.9800 |
S1—C1 | 1.807 (5) | C23—H23B | 0.9800 |
O1—C8 | 1.244 (6) | C23—H23C | 0.9800 |
O2—C8 | 1.268 (6) | C25—C26 | 1.526 (7) |
O3—C6 | 1.190 (6) | C26—C27 | 1.524 (7) |
O4—C9 | 1.221 (6) | C26—H26 | 1.0000 |
N1—C6 | 1.370 (7) | C27—C28 | 1.379 (8) |
N1—C3 | 1.415 (6) | C27—C32 | 1.387 (8) |
N1—C4 | 1.462 (6) | C28—C29 | 1.389 (8) |
N2—C9 | 1.333 (7) | C28—H28 | 0.9500 |
N2—C5 | 1.428 (6) | C29—C30 | 1.377 (9) |
N2—H2 | 0.8800 | C29—H29 | 0.9500 |
N3—C10 | 1.480 (7) | C30—C31 | 1.388 (10) |
N3—H3A | 0.9100 | C30—H30 | 0.9500 |
N3—H3B | 0.9100 | C31—C32 | 1.384 (8) |
N3—H3C | 0.9100 | C31—H31 | 0.9500 |
C1—C2 | 1.519 (7) | C32—H32 | 0.9500 |
C1—H1A | 0.9900 | S3—C36 | 1.798 (6) |
C1—H1B | 0.9900 | S3—C102 | 1.820 (15) |
C2—C3 | 1.333 (6) | S3—C33 | 1.892 (11) |
C2—C7 | 1.478 (7) | O9—C40 | 1.271 (12) |
C3—C8 | 1.495 (7) | O10—C40 | 1.207 (9) |
C4—C5 | 1.549 (7) | O11—C38 | 1.192 (7) |
C4—H4 | 1.0000 | O12—C41 | 1.208 (6) |
C5—C6 | 1.561 (7) | N7—C38 | 1.368 (8) |
C5—H5 | 1.0000 | N7—C35 | 1.407 (8) |
C7—H7A | 0.9800 | N7—C36 | 1.472 (8) |
C7—H7B | 0.9800 | N8—C41 | 1.339 (7) |
C7—H7C | 0.9800 | N8—C37 | 1.448 (7) |
C9—C10 | 1.545 (7) | N8—H8 | 0.8800 |
C10—C11 | 1.501 (7) | N9—C42 | 1.487 (7) |
C10—H10 | 1.0000 | N9—H9A | 0.9100 |
C11—C12 | 1.378 (8) | N9—H9B | 0.9100 |
C11—C16 | 1.384 (7) | N9—H9C | 0.9100 |
C12—C13 | 1.384 (9) | C33—C34 | 1.512 (17) |
C12—H12 | 0.9500 | C33—H33A | 0.9900 |
C13—C14 | 1.397 (10) | C33—H33B | 0.9900 |
C13—H13 | 0.9500 | C34—C35 | 1.294 (13) |
C14—C15 | 1.354 (10) | C34—C39 | 1.496 (17) |
C14—H14 | 0.9500 | C35—C101 | 1.455 (14) |
C15—C16 | 1.378 (8) | C35—C40 | 1.530 (13) |
C15—H15 | 0.9500 | C36—C37 | 1.541 (8) |
C16—H16 | 0.9500 | C36—H36 | 1.0000 |
S2—C17 | 1.806 (6) | C37—C38 | 1.523 (8) |
S2—C21 | 1.809 (5) | C37—H37 | 1.0000 |
O5—C24 | 1.246 (6) | C39—H39A | 0.9800 |
O6—C24 | 1.246 (6) | C39—H39B | 0.9800 |
O7—C22 | 1.208 (6) | C39—H39C | 0.9800 |
O8—C25 | 1.219 (6) | C41—C42 | 1.531 (7) |
N4—C22 | 1.367 (6) | C42—C43 | 1.527 (7) |
N4—C19 | 1.403 (6) | C42—H42 | 1.0000 |
N4—C21 | 1.466 (6) | C43—C48 | 1.371 (8) |
N5—C25 | 1.354 (6) | C43—C44 | 1.381 (8) |
N5—C20 | 1.432 (6) | C44—C45 | 1.399 (9) |
N5—H5A | 0.8800 | C44—H44 | 0.9500 |
N6—C26 | 1.482 (7) | C45—C46 | 1.350 (10) |
N6—H6A | 0.9100 | C45—H45 | 0.9500 |
N6—H6B | 0.9100 | C46—C47 | 1.374 (10) |
N6—H6C | 0.9100 | C46—H46 | 0.9500 |
C17—C18 | 1.502 (8) | C47—C48 | 1.388 (8) |
C17—H17A | 0.9900 | C47—H47 | 0.9500 |
C17—H17B | 0.9900 | C48—H48 | 0.9500 |
C18—C19 | 1.340 (7) | C100—C101 | 1.51 (2) |
C18—C23 | 1.511 (8) | C101—C102 | 1.54 (2) |
C19—C24 | 1.523 (7) | O14—O22 | 1.15 (3) |
C20—C22 | 1.533 (7) | O16—O21 | 1.67 (3) |
C20—C21 | 1.544 (6) | O17—O17i | 1.056 (12) |
C20—H20 | 1.0000 | O18—O20 | 1.04 (2) |
C21—H21 | 1.0000 | O19—O19ii | 1.646 (18) |
C4—S1—C1 | 94.1 (2) | N4—C22—C20 | 92.4 (4) |
C6—N1—C3 | 133.8 (4) | C18—C23—H23A | 109.5 |
C6—N1—C4 | 96.3 (4) | C18—C23—H23B | 109.5 |
C3—N1—C4 | 125.8 (4) | H23A—C23—H23B | 109.5 |
C9—N2—C5 | 121.9 (4) | C18—C23—H23C | 109.5 |
C9—N2—H2 | 119.0 | H23A—C23—H23C | 109.5 |
C5—N2—H2 | 119.0 | H23B—C23—H23C | 109.5 |
C10—N3—H3A | 109.5 | O6—C24—O5 | 126.5 (5) |
C10—N3—H3B | 109.5 | O6—C24—C19 | 116.4 (4) |
H3A—N3—H3B | 109.5 | O5—C24—C19 | 117.1 (4) |
C10—N3—H3C | 109.5 | O8—C25—N5 | 123.8 (5) |
H3A—N3—H3C | 109.5 | O8—C25—C26 | 121.5 (4) |
H3B—N3—H3C | 109.5 | N5—C25—C26 | 114.5 (4) |
C2—C1—S1 | 116.5 (3) | N6—C26—C27 | 112.0 (4) |
C2—C1—H1A | 108.2 | N6—C26—C25 | 106.9 (4) |
S1—C1—H1A | 108.2 | C27—C26—C25 | 107.5 (4) |
C2—C1—H1B | 108.2 | N6—C26—H26 | 110.1 |
S1—C1—H1B | 108.2 | C27—C26—H26 | 110.1 |
H1A—C1—H1B | 107.3 | C25—C26—H26 | 110.1 |
C3—C2—C7 | 123.0 (4) | C28—C27—C32 | 120.5 (5) |
C3—C2—C1 | 123.0 (4) | C28—C27—C26 | 118.6 (4) |
C7—C2—C1 | 113.9 (4) | C32—C27—C26 | 120.8 (5) |
C2—C3—N1 | 120.2 (4) | C27—C28—C29 | 119.9 (5) |
C2—C3—C8 | 127.1 (4) | C27—C28—H28 | 120.1 |
N1—C3—C8 | 112.5 (4) | C29—C28—H28 | 120.1 |
N1—C4—C5 | 87.6 (3) | C30—C29—C28 | 119.5 (5) |
N1—C4—S1 | 109.6 (3) | C30—C29—H29 | 120.3 |
C5—C4—S1 | 116.0 (3) | C28—C29—H29 | 120.3 |
N1—C4—H4 | 113.6 | C29—C30—C31 | 121.0 (5) |
C5—C4—H4 | 113.6 | C29—C30—H30 | 119.5 |
S1—C4—H4 | 113.6 | C31—C30—H30 | 119.5 |
N2—C5—C4 | 117.4 (4) | C32—C31—C30 | 119.3 (6) |
N2—C5—C6 | 116.1 (4) | C32—C31—H31 | 120.3 |
C4—C5—C6 | 85.5 (4) | C30—C31—H31 | 120.4 |
N2—C5—H5 | 111.8 | C31—C32—C27 | 119.9 (5) |
C4—C5—H5 | 111.8 | C31—C32—H32 | 120.1 |
C6—C5—H5 | 111.8 | C27—C32—H32 | 120.1 |
O3—C6—N1 | 132.8 (5) | C36—S3—C102 | 91.0 (5) |
O3—C6—C5 | 136.8 (5) | C36—S3—C33 | 96.2 (4) |
N1—C6—C5 | 90.4 (4) | C38—N7—C35 | 130.8 (6) |
C2—C7—H7A | 109.5 | C38—N7—C36 | 94.3 (4) |
C2—C7—H7B | 109.5 | C35—N7—C36 | 127.0 (5) |
H7A—C7—H7B | 109.5 | C41—N8—C37 | 122.0 (4) |
C2—C7—H7C | 109.5 | C41—N8—H8 | 119.0 |
H7A—C7—H7C | 109.5 | C37—N8—H8 | 119.0 |
H7B—C7—H7C | 109.5 | C42—N9—H9A | 109.5 |
O1—C8—O2 | 125.6 (5) | C42—N9—H9B | 109.5 |
O1—C8—C3 | 116.1 (4) | H9A—N9—H9B | 109.5 |
O2—C8—C3 | 118.3 (4) | C42—N9—H9C | 109.5 |
O4—C9—N2 | 124.1 (5) | H9A—N9—H9C | 109.5 |
O4—C9—C10 | 120.8 (5) | H9B—N9—H9C | 109.5 |
N2—C9—C10 | 114.8 (4) | C34—C33—S3 | 118.0 (7) |
N3—C10—C11 | 112.8 (4) | C34—C33—H33A | 107.8 |
N3—C10—C9 | 107.6 (4) | S3—C33—H33A | 107.8 |
C11—C10—C9 | 107.6 (4) | C34—C33—H33B | 107.8 |
N3—C10—H10 | 109.6 | S3—C33—H33B | 107.8 |
C11—C10—H10 | 109.6 | H33A—C33—H33B | 107.1 |
C9—C10—H10 | 109.6 | C35—C34—C39 | 129.8 (11) |
C12—C11—C16 | 118.7 (5) | C35—C34—C33 | 116.9 (11) |
C12—C11—C10 | 119.4 (5) | C39—C34—C33 | 110.2 (9) |
C16—C11—C10 | 121.8 (5) | C34—C35—N7 | 126.5 (8) |
C11—C12—C13 | 120.7 (6) | C34—C35—C40 | 116.2 (9) |
C11—C12—H12 | 119.6 | N7—C35—C40 | 115.1 (5) |
C13—C12—H12 | 119.7 | N7—C36—C37 | 87.3 (4) |
C12—C13—C14 | 119.5 (6) | N7—C36—S3 | 110.1 (4) |
C12—C13—H13 | 120.2 | C37—C36—S3 | 115.8 (4) |
C14—C13—H13 | 120.2 | N7—C36—H36 | 113.6 |
C15—C14—C13 | 119.6 (5) | C37—C36—H36 | 113.6 |
C15—C14—H14 | 120.2 | S3—C36—H36 | 113.6 |
C13—C14—H14 | 120.2 | N8—C37—C38 | 116.2 (4) |
C14—C15—C16 | 120.8 (6) | N8—C37—C36 | 117.6 (4) |
C14—C15—H15 | 119.6 | C38—C37—C36 | 85.7 (4) |
C16—C15—H15 | 119.6 | N8—C37—H37 | 111.7 |
C15—C16—C11 | 120.6 (5) | C38—C37—H37 | 111.7 |
C15—C16—H16 | 119.7 | C36—C37—H37 | 111.7 |
C11—C16—H16 | 119.7 | O11—C38—N7 | 132.4 (5) |
C17—S2—C21 | 93.6 (2) | O11—C38—C37 | 135.7 (5) |
C22—N4—C19 | 132.3 (4) | N7—C38—C37 | 91.9 (4) |
C22—N4—C21 | 94.1 (4) | C34—C39—H39A | 109.5 |
C19—N4—C21 | 127.1 (4) | C34—C39—H39B | 109.5 |
C25—N5—C20 | 120.4 (4) | H39A—C39—H39B | 109.5 |
C25—N5—H5A | 119.8 | C34—C39—H39C | 109.5 |
C20—N5—H5A | 119.8 | H39A—C39—H39C | 109.5 |
C26—N6—H6A | 109.5 | H39B—C39—H39C | 109.5 |
C26—N6—H6B | 109.5 | O10—C40—O9 | 126.3 (9) |
H6A—N6—H6B | 109.5 | O10—C40—C35 | 115.6 (9) |
C26—N6—H6C | 109.5 | O9—C40—C35 | 118.0 (7) |
H6A—N6—H6C | 109.5 | O12—C41—N8 | 124.5 (5) |
H6B—N6—H6C | 109.5 | O12—C41—C42 | 121.2 (5) |
C18—C17—S2 | 116.4 (3) | N8—C41—C42 | 113.8 (4) |
C18—C17—H17A | 108.2 | N9—C42—C43 | 111.2 (4) |
S2—C17—H17A | 108.2 | N9—C42—C41 | 108.4 (4) |
C18—C17—H17B | 108.2 | C43—C42—C41 | 108.0 (4) |
S2—C17—H17B | 108.2 | N9—C42—H42 | 109.7 |
H17A—C17—H17B | 107.3 | C43—C42—H42 | 109.7 |
C19—C18—C17 | 124.9 (5) | C41—C42—H42 | 109.7 |
C19—C18—C23 | 121.9 (5) | C48—C43—C44 | 120.3 (5) |
C17—C18—C23 | 113.1 (4) | C48—C43—C42 | 119.7 (5) |
C18—C19—N4 | 118.2 (4) | C44—C43—C42 | 119.9 (5) |
C18—C19—C24 | 127.0 (4) | C43—C44—C45 | 118.9 (6) |
N4—C19—C24 | 114.8 (4) | C43—C44—H44 | 120.5 |
N5—C20—C22 | 114.8 (4) | C45—C44—H44 | 120.5 |
N5—C20—C21 | 119.1 (4) | C46—C45—C44 | 119.8 (6) |
C22—C20—C21 | 84.7 (3) | C46—C45—H45 | 120.1 |
N5—C20—H20 | 111.9 | C44—C45—H45 | 120.1 |
C22—C20—H20 | 111.9 | C45—C46—C47 | 121.8 (5) |
C21—C20—H20 | 111.9 | C45—C46—H46 | 119.1 |
N4—C21—C20 | 88.2 (3) | C47—C46—H46 | 119.1 |
N4—C21—S2 | 110.3 (3) | C46—C47—C48 | 118.5 (6) |
C20—C21—S2 | 115.4 (3) | C46—C47—H47 | 120.8 |
N4—C21—H21 | 113.5 | C48—C47—H47 | 120.8 |
C20—C21—H21 | 113.5 | C43—C48—C47 | 120.5 (6) |
S2—C21—H21 | 113.5 | C43—C48—H48 | 119.8 |
O7—C22—N4 | 132.3 (5) | C47—C48—H48 | 119.8 |
O7—C22—C20 | 135.3 (4) | ||
C4—S1—C1—C2 | −49.0 (4) | C18—C19—C24—O6 | −136.2 (5) |
S1—C1—C2—C3 | 24.6 (6) | N4—C19—C24—O6 | 41.7 (6) |
S1—C1—C2—C7 | −158.5 (4) | C18—C19—C24—O5 | 44.1 (7) |
C7—C2—C3—N1 | −175.3 (4) | N4—C19—C24—O5 | −138.1 (4) |
C1—C2—C3—N1 | 1.3 (7) | C20—N5—C25—O8 | 2.5 (7) |
C7—C2—C3—C8 | −1.8 (7) | C20—N5—C25—C26 | −172.7 (4) |
C1—C2—C3—C8 | 174.8 (4) | O8—C25—C26—N6 | 27.3 (6) |
C6—N1—C3—C2 | −140.3 (5) | N5—C25—C26—N6 | −157.4 (4) |
C4—N1—C3—C2 | 11.4 (7) | O8—C25—C26—C27 | −93.1 (5) |
C6—N1—C3—C8 | 45.3 (7) | N5—C25—C26—C27 | 82.2 (5) |
C4—N1—C3—C8 | −162.9 (4) | N6—C26—C27—C28 | 131.8 (5) |
C6—N1—C4—C5 | −3.3 (4) | C25—C26—C27—C28 | −111.1 (5) |
C3—N1—C4—C5 | −163.2 (4) | N6—C26—C27—C32 | −51.9 (6) |
C6—N1—C4—S1 | 113.5 (3) | C25—C26—C27—C32 | 65.2 (6) |
C3—N1—C4—S1 | −46.4 (5) | C32—C27—C28—C29 | −1.8 (9) |
C1—S1—C4—N1 | 56.3 (4) | C26—C27—C28—C29 | 174.5 (5) |
C1—S1—C4—C5 | 153.5 (4) | C27—C28—C29—C30 | 2.6 (10) |
C9—N2—C5—C4 | 116.1 (5) | C28—C29—C30—C31 | −2.5 (11) |
C9—N2—C5—C6 | −145.0 (4) | C29—C30—C31—C32 | 1.7 (11) |
N1—C4—C5—N2 | 120.0 (4) | C30—C31—C32—C27 | −0.9 (10) |
S1—C4—C5—N2 | 9.4 (5) | C28—C27—C32—C31 | 1.0 (9) |
N1—C4—C5—C6 | 2.9 (3) | C26—C27—C32—C31 | −175.3 (6) |
S1—C4—C5—C6 | −107.8 (4) | C36—S3—C33—C34 | −47.6 (9) |
C3—N1—C6—O3 | −18.3 (9) | S3—C33—C34—C35 | 35.3 (14) |
C4—N1—C6—O3 | −175.6 (5) | S3—C33—C34—C39 | −162.8 (9) |
C3—N1—C6—C5 | 160.6 (5) | C39—C34—C35—N7 | −175.3 (11) |
C4—N1—C6—C5 | 3.3 (4) | C33—C34—C35—N7 | −17.6 (17) |
N2—C5—C6—O3 | 57.4 (8) | C102—C34—C35—N7 | −31.1 (14) |
C4—C5—C6—O3 | 175.7 (6) | C39—C34—C35—C101 | −113 (2) |
N2—C5—C6—N1 | −121.5 (4) | C33—C34—C35—C101 | 44.8 (16) |
C4—C5—C6—N1 | −3.1 (3) | C39—C34—C35—C40 | 22.1 (19) |
C2—C3—C8—O1 | −128.3 (5) | C33—C34—C35—C40 | 179.9 (9) |
N1—C3—C8—O1 | 45.6 (6) | C38—N7—C35—C34 | −117.7 (12) |
C2—C3—C8—O2 | 49.1 (7) | C36—N7—C35—C34 | 23.0 (14) |
N1—C3—C8—O2 | −137.0 (4) | C38—N7—C35—C101 | −141.6 (8) |
C5—N2—C9—O4 | 10.4 (7) | C36—N7—C35—C101 | −1.0 (11) |
C5—N2—C9—C10 | −163.5 (4) | C38—N7—C35—C40 | 45.0 (9) |
O4—C9—C10—N3 | 44.5 (6) | C36—N7—C35—C40 | −174.4 (7) |
N2—C9—C10—N3 | −141.5 (4) | C38—N7—C36—C37 | −7.0 (4) |
O4—C9—C10—C11 | −77.3 (6) | C35—N7—C36—C37 | −158.2 (6) |
N2—C9—C10—C11 | 96.7 (5) | C38—N7—C36—S3 | 109.5 (4) |
N3—C10—C11—C12 | 132.8 (5) | C35—N7—C36—S3 | −41.7 (8) |
C9—C10—C11—C12 | −108.7 (5) | C102—S3—C36—N7 | 66.6 (7) |
N3—C10—C11—C16 | −49.6 (6) | C33—S3—C36—N7 | 45.8 (6) |
C9—C10—C11—C16 | 68.9 (6) | C102—S3—C36—C37 | 163.6 (7) |
C16—C11—C12—C13 | 0.4 (8) | C33—S3—C36—C37 | 142.8 (6) |
C10—C11—C12—C13 | 178.1 (5) | C41—N8—C37—C38 | −148.2 (4) |
C11—C12—C13—C14 | 0.3 (9) | C41—N8—C37—C36 | 112.5 (6) |
C12—C13—C14—C15 | −1.7 (9) | N7—C36—C37—N8 | 123.7 (5) |
C13—C14—C15—C16 | 2.3 (9) | S3—C36—C37—N8 | 12.7 (7) |
C14—C15—C16—C11 | −1.6 (9) | N7—C36—C37—C38 | 6.3 (4) |
C12—C11—C16—C15 | 0.2 (8) | S3—C36—C37—C38 | −104.7 (5) |
C10—C11—C16—C15 | −177.4 (5) | C35—N7—C38—O11 | −23.9 (10) |
C21—S2—C17—C18 | −48.9 (4) | C36—N7—C38—O11 | −173.3 (6) |
S2—C17—C18—C19 | 24.7 (7) | C35—N7—C38—C37 | 156.6 (6) |
S2—C17—C18—C23 | −158.7 (4) | C36—N7—C38—C37 | 7.1 (4) |
C17—C18—C19—N4 | 2.9 (7) | N8—C37—C38—O11 | 55.0 (8) |
C23—C18—C19—N4 | −173.4 (4) | C36—C37—C38—O11 | 173.7 (6) |
C17—C18—C19—C24 | −179.3 (5) | N8—C37—C38—N7 | −125.5 (4) |
C23—C18—C19—C24 | 4.4 (8) | C36—C37—C38—N7 | −6.8 (4) |
C22—N4—C19—C18 | −135.7 (5) | C34—C35—C40—O10 | −147.0 (10) |
C21—N4—C19—C18 | 8.3 (7) | N7—C35—C40—O10 | 48.5 (11) |
C22—N4—C19—C24 | 46.3 (7) | C101—C35—C40—O10 | −123.2 (11) |
C21—N4—C19—C24 | −169.8 (4) | C34—C35—C40—O9 | 34.3 (13) |
C25—N5—C20—C22 | −159.5 (4) | N7—C35—C40—O9 | −130.2 (8) |
C25—N5—C20—C21 | 102.3 (5) | C101—C35—C40—O9 | 58.0 (14) |
C22—N4—C21—C20 | −6.0 (3) | C37—N8—C41—O12 | 4.6 (7) |
C19—N4—C21—C20 | −160.1 (4) | C37—N8—C41—C42 | −167.7 (4) |
C22—N4—C21—S2 | 110.5 (3) | O12—C41—C42—N9 | 38.2 (6) |
C19—N4—C21—S2 | −43.7 (5) | N8—C41—C42—N9 | −149.3 (4) |
N5—C20—C21—N4 | 120.9 (4) | O12—C41—C42—C43 | −82.4 (6) |
C22—C20—C21—N4 | 5.4 (3) | N8—C41—C42—C43 | 90.1 (5) |
N5—C20—C21—S2 | 9.2 (5) | N9—C42—C43—C48 | −43.8 (7) |
C22—C20—C21—S2 | −106.3 (3) | C41—C42—C43—C48 | 75.1 (6) |
C17—S2—C21—N4 | 54.9 (4) | N9—C42—C43—C44 | 137.6 (5) |
C17—S2—C21—C20 | 152.9 (4) | C41—C42—C43—C44 | −103.6 (6) |
C19—N4—C22—O7 | −20.9 (9) | C48—C43—C44—C45 | 0.3 (9) |
C21—N4—C22—O7 | −172.8 (5) | C42—C43—C44—C45 | 178.9 (5) |
C19—N4—C22—C20 | 158.0 (5) | C43—C44—C45—C46 | −0.8 (10) |
C21—N4—C22—C20 | 6.0 (3) | C44—C45—C46—C47 | 2.7 (11) |
N5—C20—C22—O7 | 53.4 (7) | C45—C46—C47—C48 | −4.1 (11) |
C21—C20—C22—O7 | 173.1 (6) | C44—C43—C48—C47 | −1.8 (10) |
N5—C20—C22—N4 | −125.5 (4) | C42—C43—C48—C47 | 179.6 (6) |
C21—C20—C22—N4 | −5.8 (3) | C46—C47—C48—C43 | 3.6 (11) |
Symmetry codes: (i) −x, y, −z; (ii) −x+1, y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2iii | 0.88 | 2.22 | 3.077 (5) | 165 |
N3—H3A···O2iv | 0.91 | 1.89 | 2.780 (6) | 165 |
N3—H3B···O5v | 0.91 | 1.81 | 2.711 (5) | 173 |
N3—H3C···O15 | 0.91 | 1.91 | 2.811 (7) | 171 |
N5—H5A···O3iv | 0.88 | 2.03 | 2.883 (5) | 164 |
N6—H6A···O6v | 0.91 | 1.90 | 2.781 (6) | 161 |
N6—H6B···O15 | 0.91 | 2.18 | 2.874 (8) | 133 |
N6—H6B···O11vi | 0.91 | 2.39 | 2.995 (6) | 124 |
N6—H6B···O10vi | 0.91 | 2.39 | 3.134 (8) | 139 |
N6—H6C···O19vii | 0.91 | 1.99 | 2.794 (10) | 146 |
N6—H6C···O8 | 0.91 | 2.21 | 2.683 (6) | 112 |
N6—H6C···O19vi | 0.91 | 2.27 | 2.912 (10) | 128 |
N8—H8···O13 | 0.88 | 1.96 | 2.827 (6) | 167 |
N9—H9A···O17vi | 0.91 | 1.89 | 2.779 (8) | 166 |
N9—H9A···O17viii | 0.91 | 2.47 | 3.346 (8) | 162 |
N9—H9B···O10iv | 0.91 | 1.93 | 2.799 (7) | 160 |
N9—H9C···O7ix | 0.91 | 2.22 | 2.824 (5) | 124 |
N9—H9C···O4vi | 0.91 | 2.28 | 3.061 (6) | 144 |
Symmetry codes: (iii) −x+1/2, y+1/2, −z+1; (iv) x, y+1, z; (v) x, y−1, z; (vi) −x+1/2, y+1/2, −z; (vii) x−1/2, y+1/2, z; (viii) x+1/2, y+1/2, z; (ix) −x+1/2, y−1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C16H17N3O4S·1.9H2O |
Mr | 381.88 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 150 |
a, b, c (Å) | 31.548 (2), 11.8574 (9), 15.6654 (11) |
β (°) | 112.364 (2) |
V (Å3) | 5419.3 (7) |
Z | 12 |
Radiation type | Synchrotron, λ = 0.6891 Å |
µ (mm−1) | 0.22 |
Crystal size (mm) | 0.20 × 0.05 × 0.01 |
Data collection | |
Diffractometer | Bruker AXS SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.96, 1.00 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14822, 10703, 8136 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.636 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.074, 0.193, 1.01 |
No. of reflections | 10703 |
No. of parameters | 717 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.58, −0.47 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.21 (10) |
Computer programs: SMART (Bruker, 1995), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1974), SHELXL97.
S1—C4 | 1.802 (5) | C20—C21 | 1.544 (6) |
S1—C1 | 1.807 (5) | C25—C26 | 1.526 (7) |
O1—C8 | 1.244 (6) | C26—C27 | 1.524 (7) |
O2—C8 | 1.268 (6) | C27—C28 | 1.379 (8) |
O3—C6 | 1.190 (6) | C27—C32 | 1.387 (8) |
O4—C9 | 1.221 (6) | C28—C29 | 1.389 (8) |
N1—C6 | 1.370 (7) | C29—C30 | 1.377 (9) |
N1—C3 | 1.415 (6) | C30—C31 | 1.388 (10) |
N1—C4 | 1.462 (6) | C31—C32 | 1.384 (8) |
N2—C9 | 1.333 (7) | S3—C36 | 1.798 (6) |
N2—C5 | 1.428 (6) | S3—C102 | 1.820 (15) |
N3—C10 | 1.480 (7) | S3—C33 | 1.892 (11) |
C1—C2 | 1.519 (7) | O9—C40 | 1.271 (12) |
C2—C3 | 1.333 (6) | O10—C40 | 1.207 (9) |
C2—C7 | 1.478 (7) | O11—C38 | 1.192 (7) |
C3—C8 | 1.495 (7) | O12—C41 | 1.208 (6) |
C4—C5 | 1.549 (7) | N7—C38 | 1.368 (8) |
C5—C6 | 1.561 (7) | N7—C35 | 1.407 (8) |
C9—C10 | 1.545 (7) | N7—C36 | 1.472 (8) |
C10—C11 | 1.501 (7) | N8—C41 | 1.339 (7) |
C11—C12 | 1.378 (8) | N8—C37 | 1.448 (7) |
C11—C16 | 1.384 (7) | N9—C42 | 1.487 (7) |
C12—C13 | 1.384 (9) | C33—C34 | 1.512 (17) |
C13—C14 | 1.397 (10) | C34—C35 | 1.294 (13) |
C14—C15 | 1.354 (10) | C34—C39 | 1.496 (17) |
C15—C16 | 1.378 (8) | C35—C101 | 1.455 (14) |
S2—C17 | 1.806 (6) | C35—C40 | 1.530 (13) |
S2—C21 | 1.809 (5) | C36—C37 | 1.541 (8) |
O5—C24 | 1.246 (6) | C37—C38 | 1.523 (8) |
O6—C24 | 1.246 (6) | C41—C42 | 1.531 (7) |
O7—C22 | 1.208 (6) | C42—C43 | 1.527 (7) |
O8—C25 | 1.219 (6) | C43—C48 | 1.371 (8) |
N4—C22 | 1.367 (6) | C43—C44 | 1.381 (8) |
N4—C19 | 1.403 (6) | C44—C45 | 1.399 (9) |
N4—C21 | 1.466 (6) | C45—C46 | 1.350 (10) |
N5—C25 | 1.354 (6) | C46—C47 | 1.374 (10) |
N5—C20 | 1.432 (6) | C47—C48 | 1.388 (8) |
N6—C26 | 1.482 (7) | C100—C101 | 1.51 (2) |
C17—C18 | 1.502 (8) | C101—C102 | 1.54 (2) |
C18—C19 | 1.340 (7) | O14—O22 | 1.15 (3) |
C18—C23 | 1.511 (8) | O16—O21 | 1.67 (3) |
C19—C24 | 1.523 (7) | O18—O20 | 1.04 (2) |
C20—C22 | 1.533 (7) | ||
C4—S1—C1 | 94.1 (2) | N4—C22—C20 | 92.4 (4) |
C6—N1—C3 | 133.8 (4) | O6—C24—O5 | 126.5 (5) |
C6—N1—C4 | 96.3 (4) | O6—C24—C19 | 116.4 (4) |
C3—N1—C4 | 125.8 (4) | O5—C24—C19 | 117.1 (4) |
C9—N2—C5 | 121.9 (4) | O8—C25—N5 | 123.8 (5) |
C2—C1—S1 | 116.5 (3) | O8—C25—C26 | 121.5 (4) |
C3—C2—C7 | 123.0 (4) | N5—C25—C26 | 114.5 (4) |
C3—C2—C1 | 123.0 (4) | N6—C26—C27 | 112.0 (4) |
C7—C2—C1 | 113.9 (4) | N6—C26—C25 | 106.9 (4) |
C2—C3—N1 | 120.2 (4) | C27—C26—C25 | 107.5 (4) |
C2—C3—C8 | 127.1 (4) | C28—C27—C32 | 120.5 (5) |
N1—C3—C8 | 112.5 (4) | C28—C27—C26 | 118.6 (4) |
N1—C4—C5 | 87.6 (3) | C32—C27—C26 | 120.8 (5) |
N1—C4—S1 | 109.6 (3) | C27—C28—C29 | 119.9 (5) |
C5—C4—S1 | 116.0 (3) | C30—C29—C28 | 119.5 (5) |
N2—C5—C4 | 117.4 (4) | C29—C30—C31 | 121.0 (5) |
N2—C5—C6 | 116.1 (4) | C32—C31—C30 | 119.3 (6) |
C4—C5—C6 | 85.5 (4) | C31—C32—C27 | 119.9 (5) |
O3—C6—N1 | 132.8 (5) | C36—S3—C102 | 91.0 (5) |
O3—C6—C5 | 136.8 (5) | C36—S3—C33 | 96.2 (4) |
N1—C6—C5 | 90.4 (4) | C38—N7—C35 | 130.8 (6) |
O1—C8—O2 | 125.6 (5) | C38—N7—C36 | 94.3 (4) |
O1—C8—C3 | 116.1 (4) | C35—N7—C36 | 127.0 (5) |
O2—C8—C3 | 118.3 (4) | C41—N8—C37 | 122.0 (4) |
O4—C9—N2 | 124.1 (5) | C34—C33—S3 | 118.0 (7) |
O4—C9—C10 | 120.8 (5) | C35—C34—C39 | 129.8 (11) |
N2—C9—C10 | 114.8 (4) | C35—C34—C33 | 116.9 (11) |
N3—C10—C11 | 112.8 (4) | C39—C34—C33 | 110.2 (9) |
N3—C10—C9 | 107.6 (4) | C34—C35—N7 | 126.5 (8) |
C11—C10—C9 | 107.6 (4) | C34—C35—C40 | 116.2 (9) |
C12—C11—C16 | 118.7 (5) | N7—C35—C40 | 115.1 (5) |
C12—C11—C10 | 119.4 (5) | N7—C36—C37 | 87.3 (4) |
C16—C11—C10 | 121.8 (5) | N7—C36—S3 | 110.1 (4) |
C11—C12—C13 | 120.7 (6) | C37—C36—S3 | 115.8 (4) |
C12—C13—C14 | 119.5 (6) | N8—C37—C38 | 116.2 (4) |
C15—C14—C13 | 119.6 (5) | N8—C37—C36 | 117.6 (4) |
C14—C15—C16 | 120.8 (6) | C38—C37—C36 | 85.7 (4) |
C15—C16—C11 | 120.6 (5) | O11—C38—N7 | 132.4 (5) |
C17—S2—C21 | 93.6 (2) | O11—C38—C37 | 135.7 (5) |
C22—N4—C19 | 132.3 (4) | N7—C38—C37 | 91.9 (4) |
C22—N4—C21 | 94.1 (4) | O10—C40—O9 | 126.3 (9) |
C19—N4—C21 | 127.1 (4) | O10—C40—C35 | 115.6 (9) |
C25—N5—C20 | 120.4 (4) | O9—C40—C35 | 118.0 (7) |
C18—C17—S2 | 116.4 (3) | O12—C41—N8 | 124.5 (5) |
C19—C18—C17 | 124.9 (5) | O12—C41—C42 | 121.2 (5) |
C19—C18—C23 | 121.9 (5) | N8—C41—C42 | 113.8 (4) |
C17—C18—C23 | 113.1 (4) | N9—C42—C43 | 111.2 (4) |
C18—C19—N4 | 118.2 (4) | N9—C42—C41 | 108.4 (4) |
C18—C19—C24 | 127.0 (4) | C43—C42—C41 | 108.0 (4) |
N4—C19—C24 | 114.8 (4) | C48—C43—C44 | 120.3 (5) |
N5—C20—C22 | 114.8 (4) | C48—C43—C42 | 119.7 (5) |
N5—C20—C21 | 119.1 (4) | C44—C43—C42 | 119.9 (5) |
C22—C20—C21 | 84.7 (3) | C43—C44—C45 | 118.9 (6) |
N4—C21—C20 | 88.2 (3) | C46—C45—C44 | 119.8 (6) |
N4—C21—S2 | 110.3 (3) | C45—C46—C47 | 121.8 (5) |
C20—C21—S2 | 115.4 (3) | C46—C47—C48 | 118.5 (6) |
O7—C22—N4 | 132.3 (5) | C43—C48—C47 | 120.5 (6) |
O7—C22—C20 | 135.3 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2i | 0.88 | 2.22 | 3.077 (5) | 164.9 |
N3—H3A···O2ii | 0.91 | 1.89 | 2.780 (6) | 165.2 |
N3—H3B···O5iii | 0.91 | 1.81 | 2.711 (5) | 172.8 |
N3—H3C···O15 | 0.91 | 1.91 | 2.811 (7) | 171.0 |
N5—H5A···O3ii | 0.88 | 2.03 | 2.883 (5) | 164.0 |
N6—H6A···O6iii | 0.91 | 1.90 | 2.781 (6) | 161.0 |
N6—H6B···O15 | 0.91 | 2.18 | 2.874 (8) | 133.0 |
N6—H6B···O11iv | 0.91 | 2.39 | 2.995 (6) | 124.2 |
N6—H6B···O10iv | 0.91 | 2.39 | 3.134 (8) | 138.8 |
N6—H6C···O19v | 0.91 | 1.99 | 2.794 (10) | 146.2 |
N6—H6C···O8 | 0.91 | 2.21 | 2.683 (6) | 111.9 |
N6—H6C···O19iv | 0.91 | 2.27 | 2.912 (10) | 127.5 |
N8—H8···O13 | 0.88 | 1.96 | 2.827 (6) | 166.7 |
N9—H9A···O17iv | 0.91 | 1.89 | 2.779 (8) | 165.6 |
N9—H9A···O17vi | 0.91 | 2.47 | 3.346 (8) | 162.3 |
N9—H9B···O10ii | 0.91 | 1.93 | 2.799 (7) | 160.0 |
N9—H9C···O7vii | 0.91 | 2.22 | 2.824 (5) | 123.5 |
N9—H9C···O4iv | 0.91 | 2.28 | 3.061 (6) | 144.1 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1; (ii) x, y+1, z; (iii) x, y−1, z; (iv) −x+1/2, y+1/2, −z; (v) x−1/2, y+1/2, z; (vi) x+1/2, y+1/2, z; (vii) −x+1/2, y−1/2, −z. |
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The cephalosporin derivative cephalexin (CEX) is an antibiotic useful for treating a variety of infections, including those of the respiratory tract, of the skin and of other soft tissues. The characterization of the solid-state properties of CEX has, however, been hampered by uncertainty over the exact nature of its hydration behaviour. CEX can form a range of hydrates in the solid state, all with essentially identical unit cells, and has thus been identified as part of the class of compounds known as isomorphic desolvates (Stephenson et al., 1998). Indeed, CEX is known to go further and reversibly replaces water with other small, polar, solvent molecules (Pfeiffer et al., 1970). Powder diffraction shows that the isomorphic solvates have similar unit-cell dimensions but, despite their crystallographic similarities, their commercially important physical properties (such as their solubilities and dehydration behaviour) vary considerably. Despite considerable interest in CEX, no single-crystal structure determination had previously been achieved, and so the structural basis of its ready solvation/desolvation process remained unknown. However, we have overcome the problems of small crystal size and loss of (single) crystallinity upon facile dehydration by utilizing careful sample preparation methods (see experimental section) and the extra intensity of synchrotron radiation to report here the first crystal structure of any CEX hydrate, that of CEX·1.9H2O, (I).
The asymmetic unit of (I) was found to contain three CEX molecules and, spread over ten sites, 5.72 water molecules. The three crystallographically independant molecules of CEX (Fig. 1) were found to exist in the zwitterionic form, with no significant differences in their bond lengths or angles. One CEX molecule is disordered, and so its geometric parameters are omitted from Table 2. There is some flexibility in the amide backbone, with the O—C—C—N(H3) torsion angles ranging from 27.3 (6) to 44.5 (6) °. The geometry of the related species cefadroxil (Shin & Cho, 1992) has a similar conformation, fitting within the range found here for CEX, as does CEX complexed with β- napthol (Kemperman et al., 1999), although here the amide backbone is more eclipsed (equivalent angle 16.2 °).
That the stochiometrically exact dihydrate is not found is unsurprizing, given the steep gradient observed by Stephenson et al. (1998) in the moisture adsorption isotherms of CEX. Only above 70% relative humidity does CEX begin to approach a genuine dihydrate. The structural basis of the ready transportation of water is seen in Fig. 2. The water molecules lie in a distinct channel, which zigzags along the a direction. The channel displays distinct and repeating narrow and wide sections along its length, with the narrower section (containing atoms O17 and O19) centred about a = 0 and 1/2, and the wider section about a = 0.25 and 0.75. These wide and narrow sections extend seperately along the b direction, creating a grid of channels extending throughout the ab plane. Only atom O15 appears to lie outside the channels running along b. With solvent transport blocked only in the c direction, it can easily be seen how different CEX hydrates can have similar unit cells. The water sites exist as pairs with a total occupancy of 1, except for atom O13 in the wide section, which is the only fully occupied site, and the uniquely positioned atom O15. This complex arrangement with fluctuating void spaces must have a considerable effect on the dehydration behaviour of CEX. Interpreting the hydrogen-bonding behaviour is difficult, as the H atoms of the water molecules could not be reliably placed. Table 3 shows only hydrogen-bonding involving N—H donors, but it should be remembered that there must be considerable bonding via O—H donors as well. Within these limitations, some interesting points can be raised. Firstly, only those water sites already highlighted (the narrow channel sites O15, O17 and O19, and the wholly occupied site O13) form hydrogen-bonds with amine units. It is tempting to suggest that loss of the other water molecules should be favoured, leaving, as is in fact found under ambient conditions, a compound that is approximately monohydrate. There is also a sharp change in the gradient of Stephenson's moisture adsorption isotherm, corresponding to a psuedo-stable partial hydrate (CEX.nH2O, with n = 0.25–0.35). This could be explained by further site selective stripping of water to leave perhaps only the completely occupied site O13 (giving CEX·0.33H2O) or the unique site O15 (giving CEX·0.24H2O).