Apremilast (APR), an anti-psoriatic agent, easily forms isostructural cocrystals and solvates with aromatic entities, often disobeying at the same time Kitaigorodsky's rule as to the saturation of possible hydrogen-bonding sites. In this paper the reasons for this peculiar behavior are investigated, employing a joint experimental and theoretical approach. This includes the design of cocrystals with coformers having a high propensity towards the formation of both aromatic–aromatic and hydrogen-bonding interactions, determination of their structure, using solid-state NMR spectroscopy and X-ray crystallography, as well as calculations of stabilization energies of formation of the obtained cocrystals, followed by crystal structure prediction calculations and solubility measurements. The findings indicate that the stabilization energies of cocrystal formation are positive in all cases, which results from strain in the APR conformation in these crystal forms. On the other hand, solubility measurements show that the Gibbs free energy of formation of the apremilast:picolinamide cocrystal is negative, suggesting that the formation of the studied cocrystals is entropy driven. This entropic stabilization is associated with the disorder observed in almost all known cocrystals and solvates of APR.
Supporting information
CCDC references: 1916487; 1916491; 1916488; 1916489; 1916490
For all structures, data collection: CrysAlis PRO, Agilent Technologies, Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET) (compiled Feb 9 2015,16:26:32); cell refinement: CrysAlis PRO, Agilent Technologies, Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET) (compiled Feb 9 2015,16:26:32); data reduction: CrysAlis PRO, Agilent Technologies, Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET) (compiled Feb 9 2015,16:26:32); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).
Crystal data top
C22H24N2O7S | F(000) = 1936 |
Mr = 460.49 | Dx = 1.360 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54184 Å |
a = 8.71353 (13) Å | Cell parameters from 14995 reflections |
b = 29.4960 (6) Å | θ = 2.9–74.2° |
c = 17.6717 (2) Å | µ = 1.68 mm−1 |
β = 97.9370 (14)° | T = 293 K |
V = 4498.36 (12) Å3 | 0.31 × 0.06 × 0.02 mm |
Z = 8 | |
Data collection top
SuperNova, Dual, Cu at zero, TitanS2 diffractometer | 17606 independent reflections |
Radiation source: sealed X-ray tube, SuperNova (Cu) X-ray Source | 14660 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.038 |
Detector resolution: 4.1685 pixels mm-1 | θmax = 75.4°, θmin = 2.5° |
ω scans | h = −9→10 |
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb 9 2015,16:26:32)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | k = −36→36 |
Tmin = 0.817, Tmax = 1.000 | l = −22→22 |
43359 measured reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.045 | w = 1/[σ2(Fo2) + (0.0529P)2 + 0.3705P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.119 | (Δ/σ)max < 0.001 |
S = 1.03 | Δρmax = 0.17 e Å−3 |
17606 reflections | Δρmin = −0.30 e Å−3 |
1169 parameters | Absolute structure: Flack x determined using 5723 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). |
1 restraint | Absolute structure parameter: 0.004 (8) |
Primary atom site location: structure-invariant direct methods | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1A | 1.13126 (12) | 0.24313 (4) | 0.33826 (6) | 0.0605 (3) | |
O1A | 0.7488 (4) | 0.15813 (13) | 0.3638 (2) | 0.0759 (9) | |
O2A | 1.1061 (4) | 0.21159 (11) | 0.55654 (16) | 0.0576 (7) | |
O3A | 1.3046 (7) | 0.06551 (18) | 0.7028 (3) | 0.1191 (18) | |
O4A | 1.2683 (4) | 0.26942 (18) | 0.3397 (2) | 0.0917 (12) | |
O5A | 1.1468 (6) | 0.19552 (15) | 0.3507 (3) | 0.0964 (13) | |
O6A | 0.7826 (3) | 0.34366 (12) | 0.63702 (18) | 0.0639 (8) | |
O7A | 0.4883 (3) | 0.32723 (12) | 0.6093 (2) | 0.0667 (8) | |
N1A | 0.9157 (4) | 0.19633 (11) | 0.45461 (18) | 0.0486 (7) | |
N2A | 1.2048 (5) | 0.12631 (15) | 0.6355 (2) | 0.0651 (10) | |
H2A | 1.2125 | 0.1553 | 0.6331 | 0.078* | |
C1A | 1.0956 (5) | 0.10711 (15) | 0.5807 (3) | 0.0564 (10) | |
C2A | 1.0580 (7) | 0.06036 (17) | 0.5742 (4) | 0.0740 (14) | |
H2AA | 1.1098 | 0.0398 | 0.6085 | 0.089* | |
C3A | 0.9450 (6) | 0.04523 (18) | 0.5172 (4) | 0.0768 (15) | |
H3A | 0.9208 | 0.0145 | 0.5154 | 0.092* | |
C4A | 0.8663 (6) | 0.07344 (17) | 0.4629 (3) | 0.0690 (12) | |
H4A | 0.7913 | 0.0625 | 0.4247 | 0.083* | |
C5A | 1.0138 (4) | 0.13529 (14) | 0.5259 (2) | 0.0498 (8) | |
C6A | 1.0222 (4) | 0.18512 (13) | 0.5178 (2) | 0.0468 (8) | |
C7A | 0.9051 (5) | 0.11878 (15) | 0.4685 (3) | 0.0544 (9) | |
C8A | 0.8427 (5) | 0.15768 (16) | 0.4209 (2) | 0.0554 (9) | |
C9A | 1.3031 (7) | 0.1060 (2) | 0.6935 (3) | 0.0787 (16) | |
C10A | 1.4047 (7) | 0.1378 (3) | 0.7433 (3) | 0.0933 (19) | |
H10A | 1.3515 | 0.1480 | 0.7842 | 0.140* | |
H10B | 1.4295 | 0.1634 | 0.7137 | 0.140* | |
H10C | 1.4984 | 0.1225 | 0.7640 | 0.140* | |
C11A | 0.8818 (4) | 0.24160 (14) | 0.4228 (2) | 0.0504 (8) | |
H11A | 0.8209 | 0.2371 | 0.3725 | 0.061* | |
C12A | 1.0290 (5) | 0.26663 (15) | 0.4090 (2) | 0.0559 (9) | |
H12A | 1.0984 | 0.2677 | 0.4569 | 0.067* | |
H12B | 1.0013 | 0.2976 | 0.3946 | 0.067* | |
C13A | 1.0119 (8) | 0.2526 (4) | 0.2516 (3) | 0.116 (3) | |
H13A | 0.9845 | 0.2841 | 0.2474 | 0.174* | |
H13B | 0.9196 | 0.2346 | 0.2499 | 0.174* | |
H13C | 1.0662 | 0.2442 | 0.2100 | 0.174* | |
C14A | 0.7786 (4) | 0.26766 (14) | 0.4704 (2) | 0.0486 (8) | |
C15A | 0.6204 (5) | 0.26208 (16) | 0.4531 (3) | 0.0566 (10) | |
H15A | 0.5804 | 0.2449 | 0.4108 | 0.068* | |
C16A | 0.5207 (5) | 0.28176 (16) | 0.4980 (3) | 0.0601 (10) | |
H16A | 0.4143 | 0.2777 | 0.4858 | 0.072* | |
C17A | 0.7373 (5) | 0.31566 (14) | 0.5767 (2) | 0.0506 (8) | |
C18A | 0.5782 (5) | 0.30742 (15) | 0.5610 (3) | 0.0541 (9) | |
C19A | 0.8370 (4) | 0.29491 (15) | 0.5322 (2) | 0.0519 (9) | |
H19A | 0.9434 | 0.2992 | 0.5438 | 0.062* | |
C20A | 0.9374 (5) | 0.36016 (17) | 0.6488 (3) | 0.0618 (11) | |
H20A | 0.9633 | 0.3739 | 0.6023 | 0.074* | |
H20B | 1.0091 | 0.3355 | 0.6631 | 0.074* | |
C21A | 0.9478 (7) | 0.3949 (2) | 0.7119 (3) | 0.0870 (17) | |
H21A | 0.8813 | 0.4200 | 0.6957 | 0.131* | |
H21B | 1.0528 | 0.4053 | 0.7234 | 0.131* | |
H21C | 0.9159 | 0.3814 | 0.7566 | 0.131* | |
C22A | 0.3295 (6) | 0.3142 (2) | 0.6016 (4) | 0.0872 (18) | |
H22A | 0.2736 | 0.3289 | 0.5577 | 0.131* | |
H22B | 0.2864 | 0.3231 | 0.6466 | 0.131* | |
H22C | 0.3214 | 0.2819 | 0.5955 | 0.131* | |
S1B | 0.39251 (15) | 0.45270 (5) | 0.62227 (7) | 0.0751 (3) | |
O1B | 0.7444 (4) | 0.52389 (12) | 0.59477 (19) | 0.0718 (9) | |
O2B | 0.3537 (4) | 0.50744 (11) | 0.39455 (17) | 0.0612 (7) | |
O4B | 0.3924 (7) | 0.50073 (18) | 0.6346 (3) | 0.1180 (18) | |
O5B | 0.2629 (4) | 0.4319 (3) | 0.5767 (3) | 0.123 (2) | |
O6B | 0.7389 (3) | 0.34674 (13) | 0.31471 (18) | 0.0638 (8) | |
O7B | 1.0245 (3) | 0.37108 (11) | 0.35207 (19) | 0.0602 (7) | |
N1B | 0.5556 (4) | 0.50291 (12) | 0.49455 (19) | 0.0527 (7) | |
N2B | 0.2854 (4) | 0.60340 (13) | 0.3564 (2) | 0.0598 (9) | |
H2B | 0.3242 | 0.5873 | 0.3233 | 0.072* | |
C1B | 0.3983 (5) | 0.61156 (15) | 0.4195 (2) | 0.0530 (9) | |
C2B | 0.4451 (5) | 0.65444 (16) | 0.4485 (3) | 0.0621 (10) | |
H2BA | 0.3961 | 0.6803 | 0.4267 | 0.075* | |
C3B | 0.5629 (5) | 0.65877 (16) | 0.5088 (3) | 0.0617 (10) | |
H3B | 0.5925 | 0.6877 | 0.5261 | 0.074* | |
C4B | 0.6391 (5) | 0.62136 (16) | 0.5448 (2) | 0.0573 (10) | |
H4B | 0.7188 | 0.6246 | 0.5852 | 0.069* | |
C5B | 0.5899 (5) | 0.57956 (14) | 0.5172 (2) | 0.0506 (8) | |
C7B | 0.6439 (5) | 0.53379 (15) | 0.5434 (2) | 0.0562 (10) | |
C8X | 0.4496 (5) | 0.52585 (14) | 0.4421 (2) | 0.0499 (8) | |
C8B | 0.4732 (4) | 0.57479 (14) | 0.4561 (2) | 0.0487 (8) | |
C9B | 0.1917 (6) | 0.63401 (18) | 0.3141 (3) | 0.0638 (11) | |
C10B | 0.0983 (7) | 0.6143 (2) | 0.2446 (3) | 0.0796 (14) | |
H10D | 0.1516 | 0.6189 | 0.2012 | 0.119* | |
H10E | −0.0010 | 0.6289 | 0.2360 | 0.119* | |
H10F | 0.0844 | 0.5824 | 0.2521 | 0.119* | |
C11B | 0.5566 (5) | 0.45321 (13) | 0.5003 (2) | 0.0526 (9) | |
H11B | 0.4585 | 0.4425 | 0.4721 | 0.063* | |
C12B | 0.5608 (5) | 0.43727 (15) | 0.5824 (3) | 0.0596 (10) | |
H12C | 0.6509 | 0.4502 | 0.6133 | 0.072* | |
H12D | 0.5716 | 0.4045 | 0.5841 | 0.072* | |
C13B | 0.4156 (8) | 0.4255 (2) | 0.7115 (3) | 0.0897 (17) | |
H13D | 0.4981 | 0.4397 | 0.7448 | 0.135* | |
H13E | 0.4403 | 0.3941 | 0.7050 | 0.135* | |
H13F | 0.3211 | 0.4277 | 0.7335 | 0.135* | |
C14B | 0.6856 (5) | 0.43187 (14) | 0.4624 (2) | 0.0526 (9) | |
C15B | 0.8394 (5) | 0.44239 (16) | 0.4858 (3) | 0.0619 (11) | |
H15B | 0.8661 | 0.4628 | 0.5256 | 0.074* | |
C16B | 0.9544 (5) | 0.42233 (16) | 0.4496 (3) | 0.0606 (10) | |
H16B | 1.0576 | 0.4298 | 0.4651 | 0.073* | |
C17B | 0.9180 (5) | 0.39175 (15) | 0.3917 (2) | 0.0513 (9) | |
C18B | 0.7640 (5) | 0.37933 (15) | 0.3694 (2) | 0.0508 (9) | |
C19B | 0.6489 (4) | 0.40012 (15) | 0.4047 (2) | 0.0510 (9) | |
H19B | 0.5457 | 0.3926 | 0.3894 | 0.061* | |
C20B | 0.5804 (5) | 0.33448 (19) | 0.2868 (3) | 0.0662 (12) | |
H20C | 0.5264 | 0.3599 | 0.2606 | 0.079* | |
H20D | 0.5264 | 0.3257 | 0.3290 | 0.079* | |
C21B | 0.5862 (7) | 0.2957 (2) | 0.2331 (3) | 0.0856 (17) | |
H21D | 0.6521 | 0.3033 | 0.1958 | 0.128* | |
H21E | 0.4837 | 0.2894 | 0.2079 | 0.128* | |
H21F | 0.6265 | 0.2694 | 0.2611 | 0.128* | |
C22B | 1.1824 (5) | 0.3844 (2) | 0.3698 (4) | 0.0782 (15) | |
H22D | 1.2440 | 0.3680 | 0.3380 | 0.117* | |
H22E | 1.2182 | 0.3778 | 0.4225 | 0.117* | |
H22F | 1.1915 | 0.4163 | 0.3609 | 0.117* | |
S1C | 0.86399 (12) | 0.41913 (4) | 0.11460 (6) | 0.0619 (3) | |
O1C | 1.2674 (5) | 0.34555 (14) | 0.1294 (2) | 0.0844 (11) | |
O2C | 0.9242 (4) | 0.36645 (11) | −0.08825 (18) | 0.0669 (8) | |
O3C | 0.7233 (6) | 0.20267 (15) | −0.1516 (3) | 0.0949 (12) | |
O4C | 0.8627 (6) | 0.37052 (15) | 0.1149 (3) | 0.0969 (14) | |
O5C | 0.7203 (4) | 0.44299 (19) | 0.1074 (2) | 0.0958 (14) | |
O6C | 1.2105 (3) | 0.51470 (15) | −0.18452 (19) | 0.0741 (10) | |
O7C | 1.5047 (3) | 0.50402 (13) | −0.1531 (2) | 0.0713 (9) | |
N1C | 1.1071 (4) | 0.36761 (12) | 0.0206 (2) | 0.0561 (8) | |
N2C | 0.8401 (5) | 0.27108 (15) | −0.1276 (2) | 0.0682 (10) | |
H2C | 0.8388 | 0.2987 | −0.1435 | 0.082* | |
C1C | 0.9470 (6) | 0.26152 (15) | −0.0633 (3) | 0.0600 (10) | |
C2C | 0.9871 (6) | 0.21813 (18) | −0.0355 (3) | 0.0706 (12) | |
H2CA | 0.9398 | 0.1930 | −0.0606 | 0.085* | |
C3C | 1.0953 (6) | 0.21180 (18) | 0.0281 (3) | 0.0749 (13) | |
H3C | 1.1194 | 0.1824 | 0.0446 | 0.090* | |
C4C | 1.1698 (6) | 0.24770 (18) | 0.0686 (3) | 0.0690 (12) | |
H4C | 1.2424 | 0.2431 | 0.1116 | 0.083* | |
C5C | 1.1299 (5) | 0.29068 (16) | 0.0413 (3) | 0.0598 (10) | |
C6C | 1.1819 (5) | 0.33581 (17) | 0.0713 (3) | 0.0629 (11) | |
C7C | 1.0079 (5) | 0.34650 (16) | −0.0369 (2) | 0.0550 (9) | |
C8C | 1.0226 (5) | 0.29745 (15) | −0.0235 (2) | 0.0559 (9) | |
C9C | 0.7367 (6) | 0.2423 (2) | −0.1689 (3) | 0.0721 (13) | |
C10C | 0.6422 (7) | 0.2632 (2) | −0.2373 (3) | 0.0888 (17) | |
H10G | 0.6678 | 0.2491 | −0.2829 | 0.133* | |
H10H | 0.6642 | 0.2950 | −0.2386 | 0.133* | |
H10I | 0.5341 | 0.2588 | −0.2342 | 0.133* | |
C11C | 1.1210 (5) | 0.41647 (15) | 0.0355 (2) | 0.0553 (9) | |
H11C | 1.1779 | 0.4194 | 0.0871 | 0.066* | |
C12C | 0.9629 (5) | 0.43827 (15) | 0.0386 (2) | 0.0555 (9) | |
H12E | 0.8976 | 0.4325 | −0.0095 | 0.067* | |
H12F | 0.9768 | 0.4708 | 0.0432 | 0.067* | |
C13C | 0.9756 (7) | 0.4387 (2) | 0.1986 (3) | 0.0805 (15) | |
H13G | 0.9211 | 0.4332 | 0.2413 | 0.121* | |
H13H | 0.9937 | 0.4706 | 0.1943 | 0.121* | |
H13I | 1.0729 | 0.4230 | 0.2061 | 0.121* | |
C14C | 1.2197 (5) | 0.44011 (14) | −0.0170 (2) | 0.0538 (9) | |
C15C | 1.1595 (5) | 0.46622 (16) | −0.0792 (2) | 0.0571 (10) | |
H15C | 1.0528 | 0.4695 | −0.0913 | 0.068* | |
C16C | 1.2571 (5) | 0.48744 (16) | −0.1235 (2) | 0.0554 (10) | |
C17C | 1.4177 (5) | 0.48164 (16) | −0.1062 (3) | 0.0566 (10) | |
C18C | 1.4762 (5) | 0.45574 (18) | −0.0448 (3) | 0.0635 (11) | |
H18C | 1.5828 | 0.4519 | −0.0330 | 0.076* | |
C19C | 1.3774 (5) | 0.43526 (17) | 0.0000 (3) | 0.0632 (11) | |
H19C | 1.4185 | 0.4180 | 0.0420 | 0.076* | |
C20C | 1.0496 (5) | 0.5256 (2) | −0.2021 (3) | 0.0724 (13) | |
H20E | 1.0113 | 0.5380 | −0.1575 | 0.087* | |
H20F | 0.9904 | 0.4986 | −0.2181 | 0.087* | |
C21C | 1.0330 (8) | 0.5598 (3) | −0.2654 (4) | 0.119 (3) | |
H21G | 1.0746 | 0.5477 | −0.3087 | 0.178* | |
H21H | 1.0883 | 0.5869 | −0.2483 | 0.178* | |
H21I | 0.9253 | 0.5669 | −0.2798 | 0.178* | |
C22C | 1.6688 (6) | 0.4962 (3) | −0.1402 (4) | 0.0934 (19) | |
H22G | 1.7161 | 0.5104 | −0.1801 | 0.140* | |
H22H | 1.6887 | 0.4642 | −0.1401 | 0.140* | |
H22I | 1.7114 | 0.5089 | −0.0918 | 0.140* | |
S1D | 1.58527 (13) | 0.63238 (5) | −0.17125 (6) | 0.0674 (3) | |
O1D | 1.2430 (4) | 0.70438 (11) | −0.11523 (17) | 0.0645 (8) | |
O2D | 1.6356 (3) | 0.66231 (11) | 0.07166 (15) | 0.0571 (7) | |
O3D | 1.7832 (6) | 0.81306 (15) | 0.2139 (3) | 0.0966 (14) | |
O6D | 1.2557 (3) | 0.51776 (11) | 0.14024 (17) | 0.0584 (7) | |
O4D | 1.7108 (4) | 0.60859 (18) | −0.1271 (2) | 0.0919 (13) | |
O7D | 0.9671 (3) | 0.54095 (11) | 0.1048 (2) | 0.0616 (7) | |
O5D | 1.5955 (6) | 0.68090 (17) | −0.1733 (3) | 0.0992 (14) | |
N1D | 1.4371 (4) | 0.67134 (11) | −0.02876 (18) | 0.0480 (7) | |
N2D | 1.7159 (4) | 0.75019 (14) | 0.14381 (19) | 0.0574 (8) | |
H2D | 1.7370 | 0.7219 | 0.1402 | 0.069* | |
C1D | 1.6021 (5) | 0.76709 (15) | 0.0872 (2) | 0.0514 (9) | |
C2D | 1.5577 (6) | 0.81261 (17) | 0.0773 (3) | 0.0622 (10) | |
H2DA | 1.6076 | 0.8347 | 0.1092 | 0.075* | |
C3D | 1.4397 (6) | 0.82465 (16) | 0.0202 (3) | 0.0635 (11) | |
H3D | 1.4115 | 0.8550 | 0.0152 | 0.076* | |
C4D | 1.3614 (5) | 0.79360 (16) | −0.0300 (2) | 0.0587 (10) | |
H4D | 1.2825 | 0.8024 | −0.0680 | 0.070* | |
C5D | 1.4071 (4) | 0.74881 (14) | −0.0204 (2) | 0.0489 (8) | |
C6D | 1.3476 (5) | 0.70783 (15) | −0.0627 (2) | 0.0512 (9) | |
C7D | 1.5435 (4) | 0.68655 (14) | 0.0317 (2) | 0.0473 (8) | |
C8D | 1.5241 (4) | 0.73602 (14) | 0.0363 (2) | 0.0468 (8) | |
C9D | 1.7978 (6) | 0.77241 (18) | 0.2037 (3) | 0.0634 (11) | |
C10D | 1.9046 (6) | 0.7430 (2) | 0.2561 (3) | 0.0787 (14) | |
H10J | 2.0022 | 0.7582 | 0.2691 | 0.118* | |
H10K | 1.9205 | 0.7149 | 0.2310 | 0.118* | |
H10L | 1.8597 | 0.7372 | 0.3017 | 0.118* | |
C11D | 1.4239 (4) | 0.62291 (14) | −0.0500 (2) | 0.0510 (8) | |
H11D | 1.5211 | 0.6085 | −0.0278 | 0.061* | |
C12D | 1.4111 (5) | 0.61660 (16) | −0.1364 (2) | 0.0575 (9) | |
H12G | 1.3263 | 0.6349 | −0.1613 | 0.069* | |
H12H | 1.3881 | 0.5851 | −0.1490 | 0.069* | |
C13D | 1.5627 (7) | 0.6115 (3) | −0.2647 (3) | 0.0900 (19) | |
H13J | 1.6538 | 0.6182 | −0.2876 | 0.135* | |
H13K | 1.4743 | 0.6256 | −0.2939 | 0.135* | |
H13L | 1.5475 | 0.5793 | −0.2639 | 0.135* | |
C14D | 1.2957 (5) | 0.59998 (14) | −0.0143 (2) | 0.0512 (9) | |
C15D | 1.3374 (4) | 0.56947 (14) | 0.0454 (2) | 0.0500 (8) | |
H15D | 1.4415 | 0.5627 | 0.0601 | 0.060* | |
C16D | 1.2257 (4) | 0.54907 (14) | 0.0832 (2) | 0.0476 (8) | |
C17D | 1.0702 (5) | 0.56070 (14) | 0.0620 (2) | 0.0513 (9) | |
C18D | 1.0281 (5) | 0.58973 (16) | 0.0012 (3) | 0.0599 (10) | |
H18D | 0.9241 | 0.5962 | −0.0143 | 0.072* | |
C19D | 1.1412 (5) | 0.60930 (16) | −0.0370 (3) | 0.0585 (10) | |
H19D | 1.1123 | 0.6287 | −0.0780 | 0.070* | |
C20D | 1.4164 (5) | 0.50701 (17) | 0.1659 (3) | 0.0592 (10) | |
H20G | 1.4694 | 0.5333 | 0.1900 | 0.071* | |
H20H | 1.4677 | 0.4981 | 0.1229 | 0.071* | |
C21D | 1.4200 (6) | 0.4687 (2) | 0.2221 (3) | 0.0720 (13) | |
H21J | 1.3882 | 0.4412 | 0.1955 | 0.108* | |
H21K | 1.3508 | 0.4753 | 0.2585 | 0.108* | |
H21L | 1.5234 | 0.4652 | 0.2483 | 0.108* | |
C22D | 0.8127 (5) | 0.5578 (2) | 0.0945 (4) | 0.0791 (15) | |
H22J | 0.7633 | 0.5504 | 0.0441 | 0.119* | |
H22K | 0.8145 | 0.5902 | 0.1010 | 0.119* | |
H22L | 0.7561 | 0.5443 | 0.1317 | 0.119* | |
O1 | 0.1857 (5) | 0.67368 (14) | 0.3319 (2) | 0.0841 (11) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1A | 0.0480 (5) | 0.0798 (7) | 0.0538 (5) | 0.0055 (5) | 0.0072 (4) | 0.0041 (5) |
O1A | 0.0656 (19) | 0.078 (2) | 0.078 (2) | −0.0093 (17) | −0.0105 (16) | −0.0156 (18) |
O2A | 0.0631 (17) | 0.0545 (16) | 0.0518 (14) | −0.0033 (14) | −0.0039 (13) | −0.0013 (12) |
O3A | 0.135 (4) | 0.088 (3) | 0.126 (4) | 0.027 (3) | −0.015 (3) | 0.038 (3) |
O4A | 0.0533 (18) | 0.132 (4) | 0.093 (2) | −0.017 (2) | 0.0215 (18) | −0.009 (2) |
O5A | 0.115 (3) | 0.078 (3) | 0.105 (3) | 0.034 (2) | 0.049 (3) | 0.008 (2) |
O6A | 0.0467 (15) | 0.074 (2) | 0.0714 (17) | −0.0051 (14) | 0.0087 (13) | −0.0175 (16) |
O7A | 0.0488 (15) | 0.071 (2) | 0.084 (2) | −0.0072 (14) | 0.0212 (15) | −0.0125 (17) |
N1A | 0.0483 (17) | 0.0439 (16) | 0.0520 (16) | −0.0012 (13) | 0.0018 (14) | −0.0014 (13) |
N2A | 0.071 (2) | 0.064 (2) | 0.061 (2) | 0.0139 (19) | 0.0090 (18) | 0.0144 (17) |
C1A | 0.057 (2) | 0.052 (2) | 0.064 (2) | 0.0066 (18) | 0.022 (2) | 0.0057 (18) |
C2A | 0.079 (3) | 0.048 (2) | 0.102 (4) | 0.013 (2) | 0.036 (3) | 0.014 (2) |
C3A | 0.074 (3) | 0.050 (3) | 0.113 (4) | 0.002 (2) | 0.037 (3) | −0.005 (3) |
C4A | 0.063 (3) | 0.053 (2) | 0.096 (3) | −0.011 (2) | 0.025 (2) | −0.019 (2) |
C5A | 0.0464 (19) | 0.048 (2) | 0.057 (2) | 0.0021 (16) | 0.0152 (16) | 0.0015 (16) |
C6A | 0.0475 (19) | 0.047 (2) | 0.0459 (17) | 0.0003 (16) | 0.0082 (15) | −0.0022 (15) |
C7A | 0.052 (2) | 0.047 (2) | 0.068 (2) | −0.0037 (17) | 0.0199 (18) | −0.0090 (18) |
C8A | 0.047 (2) | 0.057 (2) | 0.062 (2) | −0.0093 (18) | 0.0072 (18) | −0.0119 (19) |
C9A | 0.078 (3) | 0.095 (4) | 0.066 (3) | 0.031 (3) | 0.021 (2) | 0.021 (3) |
C10A | 0.092 (4) | 0.123 (5) | 0.062 (3) | 0.031 (4) | 0.001 (3) | 0.003 (3) |
C11A | 0.0493 (19) | 0.053 (2) | 0.0478 (18) | 0.0007 (17) | 0.0039 (15) | 0.0029 (16) |
C12A | 0.056 (2) | 0.053 (2) | 0.059 (2) | −0.0012 (18) | 0.0079 (18) | 0.0054 (17) |
C13A | 0.081 (4) | 0.213 (9) | 0.053 (3) | 0.008 (5) | 0.008 (3) | 0.012 (4) |
C14A | 0.0436 (18) | 0.049 (2) | 0.0520 (18) | −0.0002 (16) | 0.0035 (15) | 0.0060 (16) |
C15A | 0.046 (2) | 0.058 (2) | 0.064 (2) | −0.0040 (18) | 0.0036 (18) | −0.0031 (19) |
C16A | 0.0412 (19) | 0.063 (3) | 0.076 (3) | −0.0038 (18) | 0.0066 (19) | −0.004 (2) |
C17A | 0.0461 (19) | 0.051 (2) | 0.0539 (19) | 0.0001 (16) | 0.0052 (16) | 0.0002 (16) |
C18A | 0.0443 (19) | 0.053 (2) | 0.066 (2) | −0.0020 (17) | 0.0114 (18) | 0.0022 (18) |
C19A | 0.0396 (18) | 0.058 (2) | 0.057 (2) | −0.0001 (17) | 0.0014 (16) | 0.0018 (17) |
C20A | 0.050 (2) | 0.068 (3) | 0.065 (2) | −0.0027 (19) | −0.0017 (19) | −0.004 (2) |
C21A | 0.071 (3) | 0.100 (4) | 0.085 (3) | −0.004 (3) | −0.007 (3) | −0.026 (3) |
C22A | 0.051 (3) | 0.103 (4) | 0.113 (4) | −0.017 (3) | 0.031 (3) | −0.025 (4) |
S1B | 0.0646 (7) | 0.0953 (10) | 0.0656 (6) | 0.0177 (6) | 0.0103 (5) | 0.0063 (6) |
O1B | 0.0684 (19) | 0.065 (2) | 0.0736 (19) | −0.0025 (16) | −0.0182 (16) | −0.0052 (16) |
O2B | 0.0618 (17) | 0.0579 (17) | 0.0600 (15) | 0.0034 (14) | −0.0050 (13) | −0.0089 (13) |
O4B | 0.147 (4) | 0.091 (3) | 0.126 (4) | 0.053 (3) | 0.057 (3) | 0.020 (3) |
O5B | 0.0517 (19) | 0.238 (7) | 0.078 (2) | −0.006 (3) | 0.0021 (18) | −0.004 (3) |
O6B | 0.0459 (14) | 0.081 (2) | 0.0637 (16) | −0.0025 (14) | 0.0058 (13) | −0.0175 (15) |
O7B | 0.0411 (13) | 0.0632 (18) | 0.0776 (19) | −0.0006 (13) | 0.0134 (13) | 0.0032 (15) |
N1B | 0.0523 (17) | 0.0434 (16) | 0.0587 (17) | 0.0009 (14) | −0.0049 (15) | −0.0021 (14) |
N2B | 0.060 (2) | 0.058 (2) | 0.0605 (19) | 0.0094 (17) | 0.0051 (17) | 0.0019 (16) |
C1B | 0.056 (2) | 0.051 (2) | 0.055 (2) | 0.0020 (18) | 0.0177 (18) | 0.0009 (17) |
C2B | 0.064 (3) | 0.051 (2) | 0.074 (3) | 0.002 (2) | 0.018 (2) | 0.000 (2) |
C3B | 0.066 (3) | 0.051 (2) | 0.071 (3) | −0.005 (2) | 0.023 (2) | −0.008 (2) |
C4B | 0.056 (2) | 0.058 (2) | 0.059 (2) | −0.0081 (19) | 0.0133 (18) | −0.0120 (18) |
C5B | 0.051 (2) | 0.048 (2) | 0.055 (2) | −0.0033 (17) | 0.0124 (16) | −0.0067 (16) |
C7B | 0.053 (2) | 0.056 (2) | 0.058 (2) | −0.0021 (18) | 0.0025 (18) | −0.0056 (18) |
C8X | 0.049 (2) | 0.052 (2) | 0.0484 (18) | 0.0008 (17) | 0.0053 (16) | −0.0022 (16) |
C8B | 0.050 (2) | 0.047 (2) | 0.0505 (18) | 0.0024 (16) | 0.0100 (16) | −0.0015 (15) |
C9B | 0.065 (3) | 0.066 (3) | 0.062 (2) | 0.012 (2) | 0.016 (2) | 0.010 (2) |
C10B | 0.079 (3) | 0.090 (4) | 0.067 (3) | 0.011 (3) | 0.002 (2) | 0.003 (3) |
C11B | 0.0466 (19) | 0.0438 (19) | 0.065 (2) | −0.0008 (16) | 0.0002 (17) | −0.0024 (17) |
C12B | 0.057 (2) | 0.050 (2) | 0.070 (2) | 0.0036 (18) | 0.004 (2) | 0.0040 (18) |
C13B | 0.098 (4) | 0.104 (5) | 0.067 (3) | 0.001 (4) | 0.011 (3) | −0.006 (3) |
C14B | 0.049 (2) | 0.046 (2) | 0.061 (2) | −0.0046 (16) | 0.0021 (17) | 0.0009 (16) |
C15B | 0.051 (2) | 0.056 (2) | 0.077 (3) | −0.0051 (18) | −0.001 (2) | −0.012 (2) |
C16B | 0.0437 (19) | 0.058 (2) | 0.077 (3) | −0.0077 (18) | −0.0014 (19) | −0.001 (2) |
C17B | 0.0438 (19) | 0.051 (2) | 0.060 (2) | 0.0004 (16) | 0.0071 (17) | 0.0101 (17) |
C18B | 0.0457 (19) | 0.057 (2) | 0.0496 (18) | −0.0008 (17) | 0.0041 (16) | 0.0009 (16) |
C19B | 0.0380 (17) | 0.058 (2) | 0.056 (2) | −0.0014 (16) | 0.0016 (16) | 0.0003 (17) |
C20B | 0.048 (2) | 0.082 (3) | 0.065 (2) | 0.004 (2) | −0.0064 (19) | −0.010 (2) |
C21B | 0.071 (3) | 0.112 (5) | 0.070 (3) | −0.001 (3) | −0.003 (2) | −0.031 (3) |
C22B | 0.042 (2) | 0.094 (4) | 0.099 (4) | −0.005 (2) | 0.012 (2) | 0.002 (3) |
S1C | 0.0516 (5) | 0.0724 (7) | 0.0619 (6) | −0.0098 (5) | 0.0083 (4) | −0.0060 (5) |
O1C | 0.078 (2) | 0.085 (2) | 0.082 (2) | 0.000 (2) | −0.0189 (19) | 0.0138 (19) |
O2C | 0.081 (2) | 0.0585 (18) | 0.0579 (16) | 0.0023 (16) | −0.0016 (15) | −0.0014 (13) |
O3C | 0.114 (3) | 0.070 (3) | 0.103 (3) | −0.024 (2) | 0.020 (2) | −0.006 (2) |
O4C | 0.116 (3) | 0.068 (2) | 0.115 (3) | −0.037 (2) | 0.044 (3) | −0.012 (2) |
O5C | 0.0534 (18) | 0.151 (4) | 0.084 (2) | 0.016 (2) | 0.0119 (17) | 0.009 (3) |
O6C | 0.0466 (15) | 0.106 (3) | 0.0690 (18) | −0.0022 (17) | 0.0049 (14) | 0.0209 (18) |
O7C | 0.0457 (15) | 0.083 (2) | 0.087 (2) | −0.0028 (16) | 0.0166 (15) | 0.0039 (19) |
N1C | 0.0562 (19) | 0.0504 (18) | 0.0602 (18) | 0.0013 (15) | 0.0025 (16) | 0.0025 (15) |
N2C | 0.085 (3) | 0.057 (2) | 0.065 (2) | −0.008 (2) | 0.017 (2) | −0.0040 (18) |
C1C | 0.068 (3) | 0.053 (2) | 0.063 (2) | 0.002 (2) | 0.024 (2) | −0.0005 (19) |
C2C | 0.081 (3) | 0.055 (3) | 0.081 (3) | 0.000 (2) | 0.030 (3) | 0.004 (2) |
C3C | 0.080 (3) | 0.056 (3) | 0.096 (3) | 0.009 (2) | 0.035 (3) | 0.013 (3) |
C4C | 0.065 (3) | 0.064 (3) | 0.081 (3) | 0.009 (2) | 0.023 (2) | 0.020 (2) |
C5C | 0.057 (2) | 0.057 (2) | 0.069 (2) | 0.0060 (19) | 0.020 (2) | 0.008 (2) |
C6C | 0.052 (2) | 0.068 (3) | 0.068 (2) | 0.005 (2) | 0.005 (2) | 0.012 (2) |
C7C | 0.057 (2) | 0.057 (2) | 0.052 (2) | −0.0002 (19) | 0.0085 (17) | 0.0007 (17) |
C8C | 0.060 (2) | 0.050 (2) | 0.060 (2) | 0.0024 (19) | 0.0194 (19) | 0.0023 (18) |
C9C | 0.082 (3) | 0.071 (3) | 0.068 (3) | −0.011 (3) | 0.029 (2) | −0.014 (2) |
C10C | 0.093 (4) | 0.099 (4) | 0.075 (3) | −0.014 (3) | 0.014 (3) | −0.016 (3) |
C11C | 0.053 (2) | 0.055 (2) | 0.057 (2) | −0.0005 (18) | 0.0026 (17) | −0.0030 (17) |
C12C | 0.053 (2) | 0.057 (2) | 0.055 (2) | −0.0003 (18) | 0.0036 (17) | −0.0053 (17) |
C13C | 0.084 (3) | 0.099 (4) | 0.058 (2) | −0.016 (3) | 0.006 (2) | 0.007 (3) |
C14C | 0.050 (2) | 0.050 (2) | 0.060 (2) | −0.0024 (17) | 0.0053 (18) | −0.0065 (17) |
C15C | 0.044 (2) | 0.067 (3) | 0.059 (2) | −0.0033 (18) | 0.0013 (17) | −0.0032 (19) |
C16C | 0.046 (2) | 0.063 (3) | 0.057 (2) | 0.0012 (18) | 0.0058 (17) | −0.0010 (18) |
C17C | 0.0428 (19) | 0.062 (3) | 0.065 (2) | −0.0018 (18) | 0.0084 (18) | −0.011 (2) |
C18C | 0.041 (2) | 0.071 (3) | 0.078 (3) | 0.0039 (19) | 0.0060 (19) | −0.006 (2) |
C19C | 0.054 (2) | 0.062 (3) | 0.071 (3) | 0.007 (2) | 0.003 (2) | 0.000 (2) |
C20C | 0.048 (2) | 0.100 (4) | 0.066 (3) | −0.006 (2) | −0.004 (2) | 0.005 (3) |
C21C | 0.073 (4) | 0.186 (9) | 0.089 (4) | −0.010 (4) | −0.016 (3) | 0.057 (5) |
C22C | 0.047 (2) | 0.109 (5) | 0.127 (5) | 0.001 (3) | 0.020 (3) | 0.012 (4) |
S1D | 0.0565 (6) | 0.0944 (9) | 0.0502 (5) | −0.0020 (6) | 0.0038 (4) | −0.0019 (5) |
O1D | 0.0616 (17) | 0.0675 (19) | 0.0590 (16) | 0.0061 (15) | −0.0114 (14) | 0.0036 (14) |
O2D | 0.0601 (16) | 0.0565 (16) | 0.0513 (14) | 0.0058 (14) | −0.0047 (12) | 0.0008 (13) |
O3D | 0.116 (3) | 0.072 (2) | 0.091 (3) | −0.008 (2) | −0.023 (2) | −0.018 (2) |
O6D | 0.0445 (14) | 0.0655 (18) | 0.0652 (16) | 0.0059 (13) | 0.0077 (12) | 0.0143 (14) |
O4D | 0.0522 (18) | 0.158 (4) | 0.0615 (18) | 0.013 (2) | −0.0038 (15) | 0.007 (2) |
O7D | 0.0419 (14) | 0.0578 (17) | 0.087 (2) | 0.0018 (12) | 0.0141 (14) | 0.0033 (15) |
O5D | 0.112 (3) | 0.093 (3) | 0.095 (3) | −0.032 (3) | 0.025 (3) | −0.001 (2) |
N1D | 0.0502 (17) | 0.0462 (17) | 0.0458 (15) | 0.0033 (13) | 0.0003 (13) | 0.0002 (12) |
N2D | 0.0574 (19) | 0.059 (2) | 0.0544 (17) | −0.0012 (16) | 0.0028 (15) | −0.0085 (16) |
C1D | 0.050 (2) | 0.053 (2) | 0.0519 (19) | −0.0029 (17) | 0.0105 (17) | −0.0002 (16) |
C2D | 0.068 (3) | 0.054 (2) | 0.067 (2) | −0.003 (2) | 0.014 (2) | −0.0041 (19) |
C3D | 0.070 (3) | 0.048 (2) | 0.074 (3) | 0.003 (2) | 0.015 (2) | 0.003 (2) |
C4D | 0.062 (2) | 0.058 (2) | 0.057 (2) | 0.005 (2) | 0.0108 (19) | 0.0087 (19) |
C5D | 0.0497 (19) | 0.050 (2) | 0.0481 (17) | 0.0034 (17) | 0.0124 (15) | 0.0070 (16) |
C6D | 0.0479 (19) | 0.061 (2) | 0.0449 (17) | 0.0049 (18) | 0.0054 (16) | 0.0057 (16) |
C7D | 0.0462 (19) | 0.054 (2) | 0.0411 (17) | 0.0026 (16) | 0.0040 (15) | 0.0003 (15) |
C8D | 0.0480 (19) | 0.050 (2) | 0.0431 (16) | −0.0009 (16) | 0.0091 (15) | −0.0019 (15) |
C9D | 0.062 (3) | 0.069 (3) | 0.058 (2) | −0.009 (2) | 0.0045 (19) | −0.009 (2) |
C10D | 0.073 (3) | 0.092 (4) | 0.067 (3) | −0.005 (3) | −0.007 (2) | −0.005 (3) |
C11D | 0.0463 (19) | 0.051 (2) | 0.0535 (19) | 0.0021 (16) | 0.0009 (16) | −0.0020 (16) |
C12D | 0.055 (2) | 0.061 (2) | 0.054 (2) | 0.0005 (19) | −0.0006 (17) | −0.0063 (18) |
C13D | 0.082 (3) | 0.134 (6) | 0.054 (2) | 0.028 (4) | 0.006 (2) | 0.000 (3) |
C14D | 0.048 (2) | 0.048 (2) | 0.057 (2) | 0.0007 (16) | 0.0029 (17) | −0.0011 (16) |
C15D | 0.0424 (18) | 0.050 (2) | 0.057 (2) | 0.0006 (16) | 0.0047 (16) | −0.0024 (16) |
C16D | 0.0431 (18) | 0.046 (2) | 0.0526 (19) | 0.0019 (15) | 0.0033 (15) | −0.0003 (15) |
C17D | 0.0441 (19) | 0.046 (2) | 0.064 (2) | 0.0018 (16) | 0.0066 (17) | −0.0045 (17) |
C18D | 0.043 (2) | 0.056 (2) | 0.077 (3) | 0.0039 (18) | −0.0038 (19) | 0.004 (2) |
C19D | 0.051 (2) | 0.056 (2) | 0.065 (2) | 0.0027 (18) | −0.0018 (19) | 0.0057 (19) |
C20D | 0.044 (2) | 0.069 (3) | 0.061 (2) | 0.0037 (19) | −0.0035 (17) | 0.003 (2) |
C21D | 0.067 (3) | 0.084 (3) | 0.062 (2) | 0.008 (3) | −0.001 (2) | 0.013 (2) |
C22D | 0.045 (2) | 0.082 (4) | 0.112 (4) | 0.009 (2) | 0.019 (3) | 0.004 (3) |
O1 | 0.097 (3) | 0.066 (2) | 0.087 (2) | 0.023 (2) | 0.005 (2) | 0.0089 (18) |
Geometric parameters (Å, º) top
S1A—O4A | 1.421 (4) | S1C—O4C | 1.434 (4) |
S1A—O5A | 1.425 (5) | S1C—O5C | 1.427 (4) |
S1A—C12A | 1.774 (4) | S1C—C12C | 1.785 (4) |
S1A—C13A | 1.751 (5) | S1C—C13C | 1.756 (5) |
O1A—C8A | 1.209 (5) | O1C—C6C | 1.216 (6) |
O2A—C6A | 1.215 (5) | O2C—C7C | 1.232 (5) |
O3A—C9A | 1.204 (8) | O3C—C9C | 1.217 (7) |
O6A—C17A | 1.363 (5) | O6C—C16C | 1.361 (6) |
O6A—C20A | 1.422 (5) | O6C—C20C | 1.430 (6) |
O7A—C18A | 1.368 (6) | O7C—C17C | 1.367 (6) |
O7A—C22A | 1.424 (6) | O7C—C22C | 1.435 (6) |
N1A—C6A | 1.389 (5) | N1C—C6C | 1.395 (6) |
N1A—C8A | 1.398 (5) | N1C—C7C | 1.388 (5) |
N1A—C11A | 1.463 (5) | N1C—C11C | 1.467 (6) |
N2A—C1A | 1.382 (6) | N2C—C1C | 1.395 (6) |
N2A—C9A | 1.379 (6) | N2C—C9C | 1.373 (7) |
C1A—C2A | 1.418 (7) | C1C—C2C | 1.398 (7) |
C1A—C5A | 1.395 (6) | C1C—C8C | 1.387 (6) |
C2A—C3A | 1.382 (8) | C2C—C3C | 1.377 (8) |
C3A—C4A | 1.379 (8) | C3C—C4C | 1.388 (8) |
C4A—C7A | 1.380 (6) | C4C—C5C | 1.383 (7) |
C5A—C6A | 1.479 (6) | C5C—C6C | 1.480 (7) |
C5A—C7A | 1.378 (6) | C5C—C8C | 1.390 (6) |
C7A—C8A | 1.481 (7) | C7C—C8C | 1.469 (6) |
C9A—C10A | 1.492 (9) | C9C—C10C | 1.498 (9) |
C11A—C12A | 1.528 (6) | C11C—C12C | 1.528 (6) |
C11A—C14A | 1.522 (6) | C11C—C14C | 1.518 (6) |
C14A—C15A | 1.380 (6) | C14C—C15C | 1.385 (6) |
C14A—C19A | 1.395 (6) | C14C—C19C | 1.374 (6) |
C15A—C16A | 1.383 (7) | C15C—C16C | 1.382 (6) |
C16A—C18A | 1.381 (6) | C16C—C17C | 1.401 (6) |
C17A—C18A | 1.397 (6) | C17C—C18C | 1.367 (7) |
C17A—C19A | 1.391 (6) | C18C—C19C | 1.385 (7) |
C20A—C21A | 1.507 (7) | C20C—C21C | 1.499 (8) |
S1B—O4B | 1.434 (6) | S1D—O4D | 1.435 (4) |
S1B—O5B | 1.432 (5) | S1D—O5D | 1.435 (5) |
S1B—C12B | 1.771 (5) | S1D—C12D | 1.776 (5) |
S1B—C13B | 1.756 (6) | S1D—C13D | 1.747 (5) |
O1B—C7B | 1.207 (5) | O1D—C6D | 1.212 (5) |
O2B—C8X | 1.227 (5) | O2D—C7D | 1.224 (5) |
O6B—C18B | 1.359 (5) | O3D—C9D | 1.222 (7) |
O6B—C20B | 1.446 (5) | O6D—C16D | 1.366 (5) |
O7B—C17B | 1.379 (5) | O6D—C20D | 1.446 (5) |
O7B—C22B | 1.424 (5) | O7D—C17D | 1.381 (5) |
N1B—C7B | 1.408 (5) | O7D—C22D | 1.422 (5) |
N1B—C8X | 1.391 (5) | N1D—C6D | 1.413 (5) |
N1B—C11B | 1.469 (5) | N1D—C7D | 1.389 (5) |
N2B—C1B | 1.402 (6) | N1D—C11D | 1.477 (5) |
N2B—C9B | 1.368 (6) | N2D—C1D | 1.400 (5) |
C1B—C2B | 1.404 (6) | N2D—C9D | 1.360 (5) |
C1B—C8B | 1.379 (6) | C1D—C2D | 1.401 (7) |
C2B—C3B | 1.380 (7) | C1D—C8D | 1.393 (6) |
C3B—C4B | 1.395 (7) | C2D—C3D | 1.384 (7) |
C4B—C5B | 1.372 (6) | C3D—C4D | 1.386 (7) |
C5B—C7B | 1.482 (6) | C4D—C5D | 1.383 (6) |
C5B—C8B | 1.385 (6) | C5D—C6D | 1.478 (6) |
C8X—C8B | 1.474 (6) | C5D—C8D | 1.379 (5) |
C9B—C10B | 1.494 (7) | C7D—C8D | 1.472 (6) |
C9B—O1 | 1.215 (6) | C9D—C10D | 1.495 (7) |
C11B—C12B | 1.521 (6) | C11D—C12D | 1.528 (5) |
C11B—C14B | 1.522 (6) | C11D—C14D | 1.515 (6) |
C14B—C15B | 1.382 (6) | C14D—C15D | 1.395 (6) |
C14B—C19B | 1.389 (6) | C14D—C19D | 1.379 (6) |
C15B—C16B | 1.393 (7) | C15D—C16D | 1.391 (6) |
C16B—C17B | 1.368 (6) | C16D—C17D | 1.398 (5) |
C17B—C18B | 1.394 (6) | C17D—C18D | 1.383 (6) |
C18B—C19B | 1.394 (6) | C18D—C19D | 1.394 (7) |
C20B—C21B | 1.492 (7) | C20D—C21D | 1.502 (7) |
| | | |
O4A—S1A—O5A | 118.3 (3) | O4C—S1C—C12C | 108.9 (2) |
O4A—S1A—C12A | 106.1 (2) | O4C—S1C—C13C | 109.2 (3) |
O4A—S1A—C13A | 109.0 (3) | O5C—S1C—O4C | 119.1 (3) |
O5A—S1A—C12A | 108.8 (2) | O5C—S1C—C12C | 106.6 (2) |
O5A—S1A—C13A | 108.9 (4) | O5C—S1C—C13C | 106.9 (3) |
C13A—S1A—C12A | 105.0 (3) | C13C—S1C—C12C | 105.3 (2) |
C17A—O6A—C20A | 119.2 (3) | C16C—O6C—C20C | 118.8 (4) |
C18A—O7A—C22A | 117.3 (4) | C17C—O7C—C22C | 116.7 (4) |
C6A—N1A—C8A | 111.2 (3) | C6C—N1C—C11C | 121.7 (4) |
C6A—N1A—C11A | 127.1 (3) | C7C—N1C—C6C | 111.0 (4) |
C8A—N1A—C11A | 121.7 (3) | C7C—N1C—C11C | 126.9 (4) |
C9A—N2A—C1A | 129.8 (5) | C9C—N2C—C1C | 128.5 (5) |
N2A—C1A—C2A | 125.8 (4) | N2C—C1C—C2C | 125.3 (5) |
N2A—C1A—C5A | 118.6 (4) | C8C—C1C—N2C | 118.4 (4) |
C5A—C1A—C2A | 115.7 (5) | C8C—C1C—C2C | 116.3 (5) |
C3A—C2A—C1A | 120.4 (5) | C3C—C2C—C1C | 121.4 (5) |
C4A—C3A—C2A | 123.2 (5) | C2C—C3C—C4C | 122.4 (5) |
C3A—C4A—C7A | 116.2 (5) | C5C—C4C—C3C | 116.3 (5) |
C1A—C5A—C6A | 129.2 (4) | C4C—C5C—C6C | 130.5 (4) |
C7A—C5A—C1A | 122.3 (4) | C4C—C5C—C8C | 121.8 (5) |
C7A—C5A—C6A | 108.5 (4) | C8C—C5C—C6C | 107.7 (4) |
O2A—C6A—N1A | 125.7 (4) | O1C—C6C—N1C | 124.1 (5) |
O2A—C6A—C5A | 128.1 (4) | O1C—C6C—C5C | 129.5 (4) |
N1A—C6A—C5A | 106.1 (3) | N1C—C6C—C5C | 106.4 (4) |
C4A—C7A—C8A | 130.0 (4) | O2C—C7C—N1C | 124.8 (4) |
C5A—C7A—C4A | 122.1 (5) | O2C—C7C—C8C | 128.2 (4) |
C5A—C7A—C8A | 107.8 (4) | N1C—C7C—C8C | 107.0 (4) |
O1A—C8A—N1A | 124.2 (4) | C1C—C8C—C5C | 121.8 (4) |
O1A—C8A—C7A | 129.5 (4) | C1C—C8C—C7C | 130.2 (4) |
N1A—C8A—C7A | 106.3 (3) | C5C—C8C—C7C | 107.9 (4) |
O3A—C9A—N2A | 121.8 (6) | O3C—C9C—N2C | 122.6 (6) |
O3A—C9A—C10A | 123.3 (5) | O3C—C9C—C10C | 122.5 (5) |
N2A—C9A—C10A | 114.9 (5) | N2C—C9C—C10C | 114.9 (5) |
N1A—C11A—C12A | 111.9 (3) | N1C—C11C—C12C | 111.5 (3) |
N1A—C11A—C14A | 110.6 (3) | N1C—C11C—C14C | 112.4 (4) |
C14A—C11A—C12A | 114.7 (3) | C14C—C11C—C12C | 114.7 (4) |
C11A—C12A—S1A | 116.0 (3) | C11C—C12C—S1C | 115.2 (3) |
C15A—C14A—C11A | 117.8 (4) | C15C—C14C—C11C | 123.8 (4) |
C15A—C14A—C19A | 119.2 (4) | C19C—C14C—C11C | 116.9 (4) |
C19A—C14A—C11A | 123.0 (3) | C19C—C14C—C15C | 119.3 (4) |
C14A—C15A—C16A | 120.7 (4) | C16C—C15C—C14C | 120.4 (4) |
C18A—C16A—C15A | 120.4 (4) | O6C—C16C—C15C | 125.2 (4) |
O6A—C17A—C18A | 115.7 (4) | O6C—C16C—C17C | 115.1 (4) |
O6A—C17A—C19A | 124.9 (4) | C15C—C16C—C17C | 119.7 (4) |
C19A—C17A—C18A | 119.4 (4) | O7C—C17C—C16C | 115.4 (4) |
O7A—C18A—C16A | 124.2 (4) | C18C—C17C—O7C | 125.0 (4) |
O7A—C18A—C17A | 116.1 (4) | C18C—C17C—C16C | 119.6 (4) |
C16A—C18A—C17A | 119.7 (4) | C17C—C18C—C19C | 120.3 (4) |
C17A—C19A—C14A | 120.5 (4) | C14C—C19C—C18C | 120.8 (4) |
O6A—C20A—C21A | 107.4 (4) | O6C—C20C—C21C | 107.7 (5) |
O4B—S1B—C12B | 109.4 (3) | O4D—S1D—C12D | 107.9 (2) |
O4B—S1B—C13B | 108.5 (3) | O4D—S1D—C13D | 108.6 (3) |
O5B—S1B—O4B | 119.5 (4) | O5D—S1D—O4D | 117.1 (3) |
O5B—S1B—C12B | 107.3 (3) | O5D—S1D—C12D | 109.2 (3) |
O5B—S1B—C13B | 107.0 (3) | O5D—S1D—C13D | 109.0 (3) |
C13B—S1B—C12B | 103.9 (3) | C13D—S1D—C12D | 104.2 (3) |
C18B—O6B—C20B | 118.1 (3) | C16D—O6D—C20D | 117.3 (3) |
C17B—O7B—C22B | 117.6 (4) | C17D—O7D—C22D | 117.3 (4) |
C7B—N1B—C11B | 127.3 (3) | C6D—N1D—C11D | 127.5 (3) |
C8X—N1B—C7B | 110.5 (3) | C7D—N1D—C6D | 110.6 (3) |
C8X—N1B—C11B | 121.9 (3) | C7D—N1D—C11D | 121.9 (3) |
C9B—N2B—C1B | 128.4 (4) | C9D—N2D—C1D | 128.9 (4) |
N2B—C1B—C2B | 125.6 (4) | N2D—C1D—C2D | 125.9 (4) |
C8B—C1B—N2B | 118.2 (4) | C8D—C1D—N2D | 117.5 (4) |
C8B—C1B—C2B | 116.3 (4) | C8D—C1D—C2D | 116.6 (4) |
C3B—C2B—C1B | 120.9 (4) | C3D—C2D—C1D | 120.1 (4) |
C2B—C3B—C4B | 122.4 (4) | C2D—C3D—C4D | 123.1 (5) |
C5B—C4B—C3B | 116.3 (4) | C5D—C4D—C3D | 116.4 (4) |
C4B—C5B—C7B | 129.6 (4) | C4D—C5D—C6D | 130.1 (4) |
C4B—C5B—C8B | 121.8 (4) | C8D—C5D—C4D | 121.4 (4) |
C8B—C5B—C7B | 108.5 (3) | C8D—C5D—C6D | 108.5 (3) |
O1B—C7B—N1B | 125.7 (4) | O1D—C6D—N1D | 125.0 (4) |
O1B—C7B—C5B | 128.4 (4) | O1D—C6D—C5D | 129.1 (4) |
N1B—C7B—C5B | 106.0 (3) | N1D—C6D—C5D | 105.9 (3) |
O2B—C8X—N1B | 124.6 (4) | O2D—C7D—N1D | 124.7 (4) |
O2B—C8X—C8B | 127.9 (4) | O2D—C7D—C8D | 128.2 (4) |
N1B—C8X—C8B | 107.5 (3) | N1D—C7D—C8D | 107.0 (3) |
C1B—C8B—C5B | 122.3 (4) | C1D—C8D—C7D | 129.6 (4) |
C1B—C8B—C8X | 130.2 (4) | C5D—C8D—C1D | 122.3 (4) |
C5B—C8B—C8X | 107.5 (3) | C5D—C8D—C7D | 108.1 (3) |
N2B—C9B—C10B | 114.1 (5) | O3D—C9D—N2D | 122.3 (5) |
O1—C9B—N2B | 122.6 (5) | O3D—C9D—C10D | 123.1 (4) |
O1—C9B—C10B | 123.3 (5) | N2D—C9D—C10D | 114.7 (5) |
N1B—C11B—C12B | 112.0 (3) | N1D—C11D—C12D | 111.3 (3) |
N1B—C11B—C14B | 112.3 (3) | N1D—C11D—C14D | 111.2 (3) |
C12B—C11B—C14B | 111.7 (3) | C14D—C11D—C12D | 114.0 (3) |
C11B—C12B—S1B | 112.8 (3) | C11D—C12D—S1D | 111.5 (3) |
C15B—C14B—C11B | 121.4 (4) | C15D—C14D—C11D | 118.2 (3) |
C15B—C14B—C19B | 119.1 (4) | C19D—C14D—C11D | 122.4 (4) |
C19B—C14B—C11B | 119.5 (3) | C19D—C14D—C15D | 119.4 (4) |
C14B—C15B—C16B | 119.8 (4) | C16D—C15D—C14D | 121.0 (4) |
C17B—C16B—C15B | 121.1 (4) | O6D—C16D—C15D | 124.9 (3) |
O7B—C17B—C18B | 115.4 (4) | O6D—C16D—C17D | 116.3 (4) |
C16B—C17B—O7B | 124.6 (4) | C15D—C16D—C17D | 118.8 (4) |
C16B—C17B—C18B | 119.9 (4) | O7D—C17D—C16D | 115.5 (4) |
O6B—C18B—C17B | 116.2 (4) | O7D—C17D—C18D | 124.3 (4) |
O6B—C18B—C19B | 125.1 (4) | C18D—C17D—C16D | 120.2 (4) |
C19B—C18B—C17B | 118.8 (4) | C17D—C18D—C19D | 120.2 (4) |
C14B—C19B—C18B | 121.2 (4) | C14D—C19D—C18D | 120.2 (4) |
O6B—C20B—C21B | 107.1 (4) | O6D—C20D—C21D | 107.7 (4) |
Crystal data top
C22H24N2O7S·0.5(C6H6O2)·0.5(H2O) | Dx = 1.421 Mg m−3 |
Mr = 524.55 | Cu Kα radiation, λ = 1.54184 Å |
Tetragonal, P41212 | Cell parameters from 29116 reflections |
a = 12.89179 (7) Å | θ = 3.4–74.6° |
c = 29.5087 (3) Å | µ = 1.66 mm−1 |
V = 4904.29 (7) Å3 | T = 100 K |
Z = 8 | 0.48 × 0.30 × 0.16 mm |
F(000) = 2208 | |
Data collection top
SuperNova, Dual, Cu at zero, TitanS2 diffractometer | 5001 independent reflections |
Radiation source: sealed X-ray tube, SuperNova (Cu) X-ray Source | 4965 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.048 |
Detector resolution: 4.1685 pixels mm-1 | θmax = 74.8°, θmin = 3.7° |
ω scans | h = −15→15 |
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb 9 2015,16:26:32)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | k = −16→15 |
Tmin = 0.250, Tmax = 1.000 | l = −36→35 |
38451 measured reflections | |
Refinement top
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0752P)2 + 4.1347P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.047 | (Δ/σ)max = 0.001 |
wR(F2) = 0.132 | Δρmax = 0.90 e Å−3 |
S = 1.08 | Δρmin = −0.63 e Å−3 |
5001 reflections | Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
360 parameters | Extinction coefficient: 0.00080 (16) |
96 restraints | Absolute structure: Flack x determined using 1998 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.001 (6) |
Hydrogen site location: mixed | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
N1 | 0.4669 (2) | 0.6556 (2) | 0.35330 (9) | 0.0197 (5) | |
C1 | 0.2922 (3) | 0.6355 (3) | 0.45136 (11) | 0.0211 (7) | |
C2 | 0.2101 (3) | 0.5648 (3) | 0.45584 (12) | 0.0257 (7) | |
H2 | 0.1705 | 0.5646 | 0.4822 | 0.031* | |
C3 | 0.1872 (3) | 0.4948 (3) | 0.42127 (13) | 0.0295 (8) | |
H3 | 0.1319 | 0.4493 | 0.4252 | 0.035* | |
C4 | 0.2440 (3) | 0.4903 (3) | 0.38093 (12) | 0.0266 (7) | |
H4 | 0.2287 | 0.4428 | 0.3582 | 0.032* | |
C5 | 0.3240 (3) | 0.5606 (3) | 0.37703 (11) | 0.0223 (7) | |
C6 | 0.4005 (3) | 0.5761 (3) | 0.33970 (11) | 0.0217 (7) | |
C7 | 0.4378 (3) | 0.6939 (3) | 0.39592 (11) | 0.0213 (6) | |
C8 | 0.3477 (3) | 0.6319 (3) | 0.41069 (11) | 0.0213 (7) | |
O1 | 0.4068 (2) | 0.53014 (19) | 0.30370 (8) | 0.0253 (5) | |
O2 | 0.4814 (2) | 0.76488 (19) | 0.41554 (8) | 0.0247 (5) | |
C9 | 0.2822 (3) | 0.7241 (3) | 0.52649 (11) | 0.0236 (7) | |
C10 | 0.3436 (3) | 0.7970 (3) | 0.55515 (11) | 0.0283 (8) | |
H10A | 0.4042 | 0.7623 | 0.5664 | 0.043* | |
H10B | 0.3019 | 0.8199 | 0.5802 | 0.043* | |
H10C | 0.3640 | 0.8559 | 0.5373 | 0.043* | |
N2 | 0.3239 (2) | 0.7068 (2) | 0.48419 (9) | 0.0228 (6) | |
H2A | 0.3762 | 0.7449 | 0.4771 | 0.027* | |
O3 | 0.2019 (2) | 0.6829 (2) | 0.53957 (8) | 0.0286 (6) | |
C11 | 0.5484 (3) | 0.7026 (3) | 0.32499 (11) | 0.0219 (7) | |
H11 | 0.5749 | 0.7630 | 0.3415 | 0.026* | |
C12 | 0.5038 (3) | 0.7428 (3) | 0.28002 (11) | 0.0230 (7) | |
H12A | 0.4755 | 0.6846 | 0.2632 | 0.028* | |
H12B | 0.5597 | 0.7721 | 0.2622 | 0.028* | |
S1 | 0.40570 (7) | 0.83756 (7) | 0.28669 (3) | 0.0236 (2) | |
O4 | 0.4469 (2) | 0.9251 (2) | 0.31135 (9) | 0.0309 (6) | |
O5 | 0.3138 (2) | 0.7883 (2) | 0.30451 (9) | 0.0296 (6) | |
C13 | 0.3810 (3) | 0.8753 (3) | 0.23037 (13) | 0.0348 (9) | |
H13A | 0.3579 | 0.8163 | 0.2133 | 0.052* | |
H13B | 0.4434 | 0.9022 | 0.2171 | 0.052* | |
H13C | 0.3283 | 0.9278 | 0.2300 | 0.052* | |
C14 | 0.6395 (3) | 0.6302 (3) | 0.31731 (12) | 0.0225 (7) | |
C15 | 0.6528 (3) | 0.5752 (3) | 0.27652 (11) | 0.0233 (7) | |
H15 | 0.6045 | 0.5827 | 0.2533 | 0.028* | |
C16 | 0.7373 (3) | 0.5099 (3) | 0.27058 (11) | 0.0232 (7) | |
C17 | 0.8110 (3) | 0.4989 (3) | 0.30517 (12) | 0.0259 (7) | |
C18 | 0.7980 (3) | 0.5536 (3) | 0.34559 (12) | 0.0273 (7) | |
H18 | 0.8464 | 0.5467 | 0.3688 | 0.033* | |
C19 | 0.7124 (3) | 0.6185 (3) | 0.35123 (12) | 0.0251 (7) | |
H19 | 0.7043 | 0.6545 | 0.3783 | 0.030* | |
O6 | 0.7558 (2) | 0.4530 (2) | 0.23185 (9) | 0.0290 (6) | |
C20 | 0.6806 (3) | 0.4618 (3) | 0.19604 (12) | 0.0285 (8) | |
H20A | 0.6775 | 0.5328 | 0.1852 | 0.034* | |
H20B | 0.6124 | 0.4423 | 0.2070 | 0.034* | |
C21 | 0.7137 (4) | 0.3900 (4) | 0.15807 (15) | 0.0436 (10) | |
H21A | 0.6639 | 0.3934 | 0.1339 | 0.065* | |
H21B | 0.7177 | 0.3202 | 0.1693 | 0.065* | |
H21C | 0.7805 | 0.4110 | 0.1470 | 0.065* | |
O7 | 0.8923 (2) | 0.4340 (2) | 0.29598 (9) | 0.0338 (6) | |
C22 | 0.9610 (3) | 0.4118 (5) | 0.33264 (15) | 0.0474 (12) | |
H22A | 1.0149 | 0.3662 | 0.3224 | 0.071* | |
H22B | 0.9231 | 0.3792 | 0.3567 | 0.071* | |
H22C | 0.9912 | 0.4752 | 0.3435 | 0.071* | |
C51 | 0.5385 (4) | 0.5008 (4) | 0.46254 (14) | 0.0354 (18) | 0.5 |
C52 | 0.4609 (5) | 0.4479 (4) | 0.48561 (18) | 0.0262 (16) | 0.5 |
H52 | 0.4239 | 0.3955 | 0.4711 | 0.031* | 0.5 |
C53 | 0.4384 (5) | 0.4731 (5) | 0.53034 (18) | 0.049 (2) | 0.5 |
C54 | 0.4936 (5) | 0.5514 (5) | 0.55199 (15) | 0.0381 (19) | 0.5 |
H54 | 0.4785 | 0.5683 | 0.5819 | 0.046* | 0.5 |
C55 | 0.5712 (6) | 0.6044 (6) | 0.5289 (2) | 0.051 (3) | 0.5 |
H55 | 0.6082 | 0.6567 | 0.5434 | 0.061* | 0.5 |
C56 | 0.5937 (5) | 0.5791 (6) | 0.4842 (2) | 0.0323 (17) | 0.5 |
H56 | 0.6457 | 0.6145 | 0.4688 | 0.039* | 0.5 |
O51 | 0.5543 (6) | 0.4722 (7) | 0.4189 (3) | 0.063 (2) | 0.5 |
H51 | 0.6152 | 0.4820 | 0.4121 | 0.094* | 0.5 |
O53 | 0.3633 (6) | 0.4238 (7) | 0.5488 (3) | 0.069 (2) | 0.5 |
H53 | 0.3415 | 0.3798 | 0.5311 | 0.083* | 0.5 |
O1W | 0.2757 (4) | 0.2757 (4) | 0.5000 | 0.0712 (16) | |
H1WA | 0.2117 | 0.2832 | 0.4939 | 0.085* | 0.5 |
H1WB | 0.2831 | 0.2118 | 0.5062 | 0.085* | 0.5 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0220 (13) | 0.0205 (13) | 0.0166 (12) | −0.0002 (11) | −0.0002 (10) | −0.0012 (10) |
C1 | 0.0218 (16) | 0.0215 (16) | 0.0200 (15) | 0.0034 (12) | −0.0016 (12) | −0.0017 (12) |
C2 | 0.0255 (17) | 0.0250 (17) | 0.0267 (16) | −0.0010 (13) | 0.0023 (13) | 0.0005 (13) |
C3 | 0.0264 (18) | 0.0273 (18) | 0.0348 (18) | −0.0054 (14) | 0.0017 (15) | −0.0039 (15) |
C4 | 0.0283 (18) | 0.0254 (17) | 0.0262 (16) | −0.0018 (14) | −0.0004 (14) | −0.0041 (14) |
C5 | 0.0239 (17) | 0.0210 (15) | 0.0221 (14) | 0.0020 (13) | −0.0017 (13) | −0.0004 (13) |
C6 | 0.0248 (16) | 0.0188 (15) | 0.0215 (15) | 0.0003 (13) | −0.0041 (13) | 0.0001 (12) |
C7 | 0.0241 (16) | 0.0216 (15) | 0.0181 (14) | 0.0026 (12) | −0.0022 (12) | 0.0009 (12) |
C8 | 0.0219 (16) | 0.0226 (16) | 0.0194 (15) | 0.0030 (12) | −0.0026 (13) | 0.0011 (12) |
O1 | 0.0317 (13) | 0.0235 (12) | 0.0207 (11) | −0.0004 (10) | −0.0011 (10) | −0.0050 (10) |
O2 | 0.0255 (12) | 0.0280 (12) | 0.0205 (11) | −0.0051 (10) | −0.0008 (9) | −0.0051 (10) |
C9 | 0.0268 (17) | 0.0263 (17) | 0.0178 (14) | 0.0030 (13) | −0.0011 (13) | −0.0010 (13) |
C10 | 0.0308 (18) | 0.0335 (19) | 0.0208 (15) | −0.0004 (15) | −0.0017 (14) | −0.0051 (14) |
N2 | 0.0220 (14) | 0.0263 (15) | 0.0199 (12) | −0.0032 (11) | 0.0020 (11) | −0.0028 (11) |
O3 | 0.0287 (13) | 0.0344 (14) | 0.0226 (11) | −0.0035 (11) | 0.0046 (10) | 0.0005 (10) |
C11 | 0.0231 (16) | 0.0217 (16) | 0.0208 (14) | −0.0026 (13) | −0.0002 (13) | −0.0006 (12) |
C12 | 0.0278 (17) | 0.0228 (16) | 0.0185 (14) | 0.0015 (12) | 0.0012 (13) | 0.0014 (12) |
S1 | 0.0245 (4) | 0.0246 (4) | 0.0216 (4) | 0.0041 (3) | 0.0012 (3) | 0.0020 (3) |
O4 | 0.0345 (14) | 0.0254 (13) | 0.0327 (13) | 0.0034 (11) | 0.0012 (11) | −0.0047 (11) |
O5 | 0.0232 (13) | 0.0359 (14) | 0.0297 (12) | 0.0021 (11) | 0.0029 (10) | 0.0040 (11) |
C13 | 0.036 (2) | 0.039 (2) | 0.0299 (19) | 0.0064 (16) | −0.0005 (16) | 0.0104 (16) |
C14 | 0.0237 (17) | 0.0233 (16) | 0.0205 (15) | −0.0023 (13) | −0.0010 (12) | 0.0012 (12) |
C15 | 0.0229 (16) | 0.0258 (17) | 0.0211 (15) | 0.0010 (13) | −0.0042 (13) | −0.0013 (13) |
C16 | 0.0255 (17) | 0.0218 (16) | 0.0225 (15) | 0.0007 (13) | 0.0008 (13) | −0.0010 (13) |
C17 | 0.0212 (16) | 0.0278 (17) | 0.0286 (17) | 0.0021 (13) | 0.0015 (13) | 0.0052 (14) |
C18 | 0.0242 (17) | 0.0329 (19) | 0.0249 (16) | −0.0022 (14) | −0.0031 (14) | 0.0060 (14) |
C19 | 0.0240 (17) | 0.0301 (18) | 0.0212 (15) | −0.0015 (13) | −0.0013 (13) | 0.0018 (14) |
O6 | 0.0289 (13) | 0.0307 (13) | 0.0272 (12) | 0.0061 (11) | −0.0004 (10) | −0.0038 (10) |
C20 | 0.0233 (17) | 0.0343 (19) | 0.0279 (17) | 0.0011 (14) | −0.0016 (14) | −0.0036 (15) |
C21 | 0.041 (2) | 0.050 (3) | 0.039 (2) | 0.005 (2) | −0.0010 (19) | −0.017 (2) |
O7 | 0.0273 (14) | 0.0423 (16) | 0.0318 (13) | 0.0133 (11) | 0.0016 (11) | 0.0081 (12) |
C22 | 0.030 (2) | 0.077 (3) | 0.035 (2) | 0.024 (2) | 0.0043 (17) | 0.023 (2) |
C51 | 0.033 (3) | 0.033 (3) | 0.040 (3) | 0.001 (2) | −0.002 (2) | 0.003 (2) |
C52 | 0.022 (2) | 0.024 (2) | 0.032 (3) | 0.0000 (19) | −0.001 (2) | 0.009 (2) |
C53 | 0.050 (3) | 0.049 (3) | 0.050 (3) | 0.000 (2) | −0.001 (2) | 0.001 (2) |
C54 | 0.042 (3) | 0.041 (3) | 0.031 (3) | 0.001 (2) | −0.001 (2) | 0.001 (2) |
C55 | 0.051 (3) | 0.050 (3) | 0.051 (3) | −0.001 (2) | −0.002 (2) | −0.001 (2) |
C56 | 0.028 (2) | 0.031 (3) | 0.038 (3) | 0.001 (2) | 0.000 (2) | 0.003 (2) |
O51 | 0.054 (4) | 0.057 (4) | 0.077 (4) | 0.000 (3) | 0.001 (4) | −0.002 (4) |
O53 | 0.057 (4) | 0.066 (4) | 0.084 (5) | −0.006 (3) | 0.001 (4) | 0.014 (4) |
O1W | 0.066 (2) | 0.066 (2) | 0.082 (4) | 0.001 (3) | −0.008 (2) | 0.008 (2) |
Geometric parameters (Å, º) top
N1—C6 | 1.395 (4) | S1—O5 | 1.444 (3) |
N1—C7 | 1.402 (4) | S1—C13 | 1.760 (4) |
N1—C11 | 1.473 (4) | C14—C15 | 1.407 (5) |
C1—C2 | 1.404 (5) | C14—C19 | 1.381 (5) |
C1—C8 | 1.398 (5) | C15—C16 | 1.388 (5) |
C1—N2 | 1.397 (4) | C16—C17 | 1.402 (5) |
C2—C3 | 1.393 (5) | C16—O6 | 1.379 (4) |
C3—C4 | 1.399 (5) | C17—C18 | 1.396 (5) |
C4—C5 | 1.378 (5) | C17—O7 | 1.367 (4) |
C5—C6 | 1.491 (5) | C18—C19 | 1.395 (5) |
C5—C8 | 1.387 (5) | O6—C20 | 1.438 (4) |
C6—O1 | 1.219 (4) | C20—C21 | 1.514 (5) |
C7—C8 | 1.476 (5) | O7—C22 | 1.427 (5) |
C7—O2 | 1.220 (4) | C51—C52 | 1.3900 |
C9—C10 | 1.492 (5) | C51—C56 | 1.3900 |
C9—N2 | 1.377 (4) | C51—O51 | 1.356 (8) |
C9—O3 | 1.226 (5) | C52—C53 | 1.3900 |
C11—C12 | 1.536 (4) | C53—C54 | 1.3900 |
C11—C14 | 1.518 (5) | C53—O53 | 1.280 (7) |
C12—S1 | 1.770 (4) | C54—C55 | 1.3900 |
S1—O4 | 1.444 (3) | C55—C56 | 1.3900 |
| | | |
C6—N1—C7 | 110.6 (3) | O4—S1—O5 | 117.53 (16) |
C6—N1—C11 | 125.3 (3) | O4—S1—C13 | 109.05 (19) |
C7—N1—C11 | 123.7 (3) | O5—S1—C12 | 108.87 (16) |
C8—C1—C2 | 116.5 (3) | O5—S1—C13 | 108.47 (19) |
N2—C1—C2 | 125.6 (3) | C13—S1—C12 | 102.40 (17) |
N2—C1—C8 | 117.9 (3) | C15—C14—C11 | 122.1 (3) |
C3—C2—C1 | 120.7 (3) | C19—C14—C11 | 119.1 (3) |
C2—C3—C4 | 122.7 (3) | C19—C14—C15 | 118.8 (3) |
C5—C4—C3 | 115.8 (3) | C16—C15—C14 | 120.6 (3) |
C4—C5—C6 | 130.1 (3) | C15—C16—C17 | 120.1 (3) |
C4—C5—C8 | 122.7 (3) | O6—C16—C15 | 124.2 (3) |
C8—C5—C6 | 107.1 (3) | O6—C16—C17 | 115.6 (3) |
N1—C6—C5 | 107.0 (3) | C18—C17—C16 | 119.3 (3) |
O1—C6—N1 | 124.5 (3) | O7—C17—C16 | 115.9 (3) |
O1—C6—C5 | 128.5 (3) | O7—C17—C18 | 124.8 (3) |
N1—C7—C8 | 106.6 (3) | C19—C18—C17 | 120.0 (3) |
O2—C7—N1 | 124.5 (3) | C14—C19—C18 | 121.2 (3) |
O2—C7—C8 | 129.0 (3) | C16—O6—C20 | 116.8 (3) |
C1—C8—C7 | 129.7 (3) | O6—C20—C21 | 107.8 (3) |
C5—C8—C1 | 121.6 (3) | C17—O7—C22 | 116.6 (3) |
C5—C8—C7 | 108.7 (3) | C52—C51—C56 | 120.0 |
N2—C9—C10 | 114.1 (3) | O51—C51—C52 | 116.1 (5) |
O3—C9—C10 | 122.8 (3) | O51—C51—C56 | 123.9 (5) |
O3—C9—N2 | 123.0 (3) | C51—C52—C53 | 120.0 |
C9—N2—C1 | 128.4 (3) | C54—C53—C52 | 120.0 |
N1—C11—C12 | 111.2 (3) | O53—C53—C52 | 116.4 (6) |
N1—C11—C14 | 112.6 (3) | O53—C53—C54 | 123.5 (6) |
C14—C11—C12 | 111.6 (3) | C53—C54—C55 | 120.0 |
C11—C12—S1 | 113.8 (2) | C56—C55—C54 | 120.0 |
O4—S1—C12 | 109.45 (17) | C55—C56—C51 | 120.0 |
Crystal data top
C22H24N2O7S·0.5(C6H6N2O) | Dx = 1.420 Mg m−3 |
Mr = 521.55 | Cu Kα radiation, λ = 1.54184 Å |
Tetragonal, P41212 | Cell parameters from 32527 reflections |
a = 12.81222 (8) Å | θ = 3.4–75.2° |
c = 29.7274 (3) Å | µ = 1.65 mm−1 |
V = 4879.84 (7) Å3 | T = 100 K |
Z = 8 | 0.41 × 0.28 × 0.25 mm |
F(000) = 2192 | |
Data collection top
SuperNova, Dual, Cu at zero, TitanS2 diffractometer | 4980 independent reflections |
Radiation source: sealed X-ray tube, SuperNova (Cu) X-ray Source | 4953 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.021 |
Detector resolution: 4.1685 pixels mm-1 | θmax = 75.2°, θmin = 3.8° |
ω scans | h = −16→16 |
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb 9 2015,16:26:32)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | k = −15→16 |
Tmin = 0.746, Tmax = 1.000 | l = −26→36 |
38165 measured reflections | |
Refinement top
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0952P)2 + 6.1533P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.058 | (Δ/σ)max = 0.001 |
wR(F2) = 0.160 | Δρmax = 1.06 e Å−3 |
S = 1.07 | Δρmin = −0.63 e Å−3 |
4980 reflections | Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
363 parameters | Extinction coefficient: 0.0009 (2) |
115 restraints | Absolute structure: Flack x determined using 2008 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.002 (4) |
Hydrogen site location: inferred from neighbouring sites | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
N1 | 0.4639 (3) | 0.6556 (3) | 0.35308 (11) | 0.0217 (7) | |
C1 | 0.2910 (3) | 0.6329 (3) | 0.45080 (14) | 0.0226 (8) | |
C2 | 0.2070 (3) | 0.5623 (3) | 0.45511 (14) | 0.0266 (9) | |
H2 | 0.1675 | 0.5615 | 0.4814 | 0.032* | |
C3 | 0.1831 (3) | 0.4941 (3) | 0.42044 (15) | 0.0288 (9) | |
H3 | 0.1268 | 0.4491 | 0.4241 | 0.035* | |
C4 | 0.2395 (3) | 0.4899 (3) | 0.38036 (15) | 0.0273 (9) | |
H4 | 0.2229 | 0.4432 | 0.3575 | 0.033* | |
C5 | 0.3218 (3) | 0.5594 (3) | 0.37665 (13) | 0.0231 (8) | |
C6 | 0.3971 (3) | 0.5762 (3) | 0.33938 (13) | 0.0220 (8) | |
C7 | 0.4378 (3) | 0.6910 (3) | 0.39614 (12) | 0.0215 (8) | |
C8 | 0.3460 (3) | 0.6293 (3) | 0.41090 (13) | 0.0215 (8) | |
O1 | 0.4021 (2) | 0.5308 (2) | 0.30346 (10) | 0.0274 (6) | |
O2 | 0.4830 (2) | 0.7608 (2) | 0.41635 (10) | 0.0263 (6) | |
C9 | 0.2815 (3) | 0.7206 (3) | 0.52621 (13) | 0.0241 (8) | |
C10 | 0.3442 (4) | 0.7931 (4) | 0.55460 (14) | 0.0301 (9) | |
H10A | 0.4044 | 0.7571 | 0.5659 | 0.045* | |
H10B | 0.3024 | 0.8171 | 0.5793 | 0.045* | |
H10C | 0.3661 | 0.8517 | 0.5368 | 0.045* | |
N2 | 0.3233 (3) | 0.7030 (3) | 0.48401 (11) | 0.0239 (7) | |
H2A | 0.3767 | 0.7405 | 0.4772 | 0.029* | |
O3 | 0.2012 (2) | 0.6787 (2) | 0.53907 (10) | 0.0302 (7) | |
C11 | 0.5461 (3) | 0.7040 (3) | 0.32535 (13) | 0.0229 (8) | |
H11 | 0.5720 | 0.7651 | 0.3418 | 0.027* | |
C12 | 0.5014 (3) | 0.7429 (3) | 0.28044 (13) | 0.0249 (8) | |
H12A | 0.4726 | 0.6840 | 0.2641 | 0.030* | |
H12B | 0.5578 | 0.7717 | 0.2625 | 0.030* | |
S1 | 0.40293 (8) | 0.83929 (8) | 0.28677 (3) | 0.0239 (3) | |
O4 | 0.4442 (3) | 0.9256 (2) | 0.31231 (11) | 0.0318 (7) | |
O5 | 0.3085 (2) | 0.7906 (3) | 0.30279 (11) | 0.0313 (7) | |
C13 | 0.3824 (4) | 0.8798 (4) | 0.23078 (16) | 0.0367 (11) | |
H13A | 0.3652 | 0.8204 | 0.2126 | 0.055* | |
H13B | 0.4448 | 0.9119 | 0.2195 | 0.055* | |
H13C | 0.3261 | 0.9292 | 0.2299 | 0.055* | |
C14 | 0.6389 (3) | 0.6310 (3) | 0.31758 (14) | 0.0235 (8) | |
C15 | 0.6532 (3) | 0.5773 (3) | 0.27696 (13) | 0.0239 (8) | |
H15 | 0.6048 | 0.5850 | 0.2539 | 0.029* | |
C16 | 0.7393 (3) | 0.5124 (3) | 0.27091 (14) | 0.0238 (8) | |
C17 | 0.8121 (3) | 0.5021 (3) | 0.30596 (14) | 0.0248 (8) | |
C18 | 0.7979 (3) | 0.5551 (3) | 0.34571 (14) | 0.0262 (8) | |
H18 | 0.8463 | 0.5479 | 0.3688 | 0.031* | |
C19 | 0.7106 (3) | 0.6201 (3) | 0.35169 (14) | 0.0269 (9) | |
H19 | 0.7014 | 0.6556 | 0.3787 | 0.032* | |
O6 | 0.7579 (2) | 0.4561 (2) | 0.23242 (10) | 0.0283 (7) | |
C20 | 0.6800 (3) | 0.4621 (4) | 0.19772 (15) | 0.0292 (9) | |
H20A | 0.6776 | 0.5322 | 0.1854 | 0.035* | |
H20B | 0.6118 | 0.4457 | 0.2101 | 0.035* | |
C21 | 0.7076 (4) | 0.3851 (4) | 0.16123 (16) | 0.0394 (11) | |
H21A | 0.6525 | 0.3830 | 0.1394 | 0.059* | |
H21B | 0.7166 | 0.3171 | 0.1742 | 0.059* | |
H21C | 0.7713 | 0.4064 | 0.1469 | 0.059* | |
O7 | 0.8954 (2) | 0.4374 (3) | 0.29705 (10) | 0.0309 (7) | |
C22 | 0.9654 (4) | 0.4194 (5) | 0.33412 (16) | 0.0402 (12) | |
H22A | 1.0188 | 0.3712 | 0.3251 | 0.060* | |
H22B | 0.9271 | 0.3909 | 0.3590 | 0.060* | |
H22C | 0.9969 | 0.4842 | 0.3430 | 0.060* | |
C51 | 0.4344 (8) | 0.4863 (9) | 0.5361 (3) | 0.091 (3) | 0.5 |
N52 | 0.4653 (9) | 0.4614 (8) | 0.4925 (3) | 0.055 (3) | 0.5 |
C53 | 0.5473 (8) | 0.5152 (9) | 0.4725 (3) | 0.073 (3) | 0.5 |
H53 | 0.5680 | 0.4985 | 0.4434 | 0.087* | 0.5 |
C54 | 0.5984 (10) | 0.5938 (11) | 0.4960 (4) | 0.086 (3) | 0.5 |
H54 | 0.6533 | 0.6298 | 0.4826 | 0.103* | 0.5 |
C55 | 0.5675 (11) | 0.6188 (10) | 0.5395 (4) | 0.101 (4) | 0.5 |
H55 | 0.6017 | 0.6714 | 0.5553 | 0.122* | 0.5 |
C56 | 0.4855 (9) | 0.5650 (9) | 0.5596 (3) | 0.095 (4) | 0.5 |
H56 | 0.4648 | 0.5817 | 0.5887 | 0.114* | 0.5 |
C57 | 0.3670 (10) | 0.4342 (11) | 0.5471 (5) | 0.120 (5) | 0.5 |
N0AA | 0.3326 (13) | 0.3584 (11) | 0.5151 (5) | 0.113 (6) | 0.5 |
H0AA | 0.3625 | 0.3542 | 0.4892 | 0.135* | 0.5 |
H0AB | 0.2820 | 0.3170 | 0.5217 | 0.135* | 0.5 |
O1AA | 0.317 (2) | 0.424 (2) | 0.5829 (7) | 0.251 (10) | 0.5 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0253 (17) | 0.0211 (15) | 0.0188 (15) | −0.0002 (13) | −0.0007 (13) | −0.0002 (13) |
C1 | 0.0234 (19) | 0.0205 (18) | 0.0240 (19) | 0.0028 (15) | −0.0036 (15) | −0.0001 (14) |
C2 | 0.025 (2) | 0.027 (2) | 0.028 (2) | −0.0003 (16) | 0.0013 (16) | −0.0011 (16) |
C3 | 0.028 (2) | 0.024 (2) | 0.034 (2) | −0.0026 (17) | −0.0010 (17) | −0.0018 (17) |
C4 | 0.028 (2) | 0.0238 (19) | 0.030 (2) | −0.0003 (17) | −0.0024 (17) | −0.0057 (16) |
C5 | 0.0258 (19) | 0.0201 (17) | 0.0233 (18) | 0.0027 (15) | −0.0034 (15) | −0.0007 (15) |
C6 | 0.0278 (19) | 0.0192 (18) | 0.0189 (18) | 0.0030 (15) | −0.0061 (15) | −0.0013 (14) |
C7 | 0.0247 (19) | 0.0212 (18) | 0.0185 (17) | 0.0025 (14) | −0.0013 (14) | −0.0012 (14) |
C8 | 0.0236 (18) | 0.0202 (17) | 0.0209 (18) | 0.0020 (14) | −0.0028 (15) | 0.0001 (14) |
O1 | 0.0355 (16) | 0.0249 (15) | 0.0217 (13) | 0.0010 (12) | −0.0020 (12) | −0.0036 (11) |
O2 | 0.0263 (14) | 0.0296 (15) | 0.0228 (13) | −0.0037 (11) | −0.0019 (11) | −0.0052 (12) |
C9 | 0.026 (2) | 0.0253 (19) | 0.0213 (18) | 0.0018 (15) | −0.0005 (15) | −0.0007 (15) |
C10 | 0.034 (2) | 0.033 (2) | 0.0230 (19) | −0.0033 (18) | 0.0009 (18) | −0.0053 (17) |
N2 | 0.0237 (17) | 0.0268 (17) | 0.0212 (16) | −0.0032 (13) | 0.0023 (13) | −0.0053 (13) |
O3 | 0.0310 (15) | 0.0333 (16) | 0.0263 (15) | −0.0059 (13) | 0.0051 (12) | 0.0011 (13) |
C11 | 0.0224 (18) | 0.0248 (19) | 0.0215 (18) | −0.0010 (15) | −0.0004 (15) | 0.0006 (15) |
C12 | 0.030 (2) | 0.0242 (19) | 0.0204 (18) | 0.0024 (15) | 0.0008 (16) | 0.0018 (15) |
S1 | 0.0250 (5) | 0.0234 (5) | 0.0232 (5) | 0.0043 (4) | 0.0017 (4) | 0.0008 (4) |
O4 | 0.0352 (16) | 0.0256 (15) | 0.0346 (16) | 0.0032 (12) | −0.0013 (13) | −0.0053 (13) |
O5 | 0.0253 (15) | 0.0341 (16) | 0.0345 (16) | 0.0009 (12) | 0.0068 (13) | −0.0013 (13) |
C13 | 0.039 (3) | 0.039 (3) | 0.032 (2) | 0.006 (2) | −0.0024 (19) | 0.0097 (19) |
C14 | 0.027 (2) | 0.0223 (19) | 0.0211 (18) | 0.0021 (16) | −0.0009 (15) | 0.0003 (14) |
C15 | 0.0237 (19) | 0.0251 (19) | 0.0230 (19) | 0.0029 (15) | −0.0050 (15) | −0.0016 (15) |
C16 | 0.0243 (19) | 0.0223 (19) | 0.0249 (19) | −0.0011 (15) | −0.0004 (15) | −0.0020 (15) |
C17 | 0.0214 (19) | 0.0252 (19) | 0.028 (2) | 0.0007 (15) | −0.0022 (15) | 0.0020 (16) |
C18 | 0.0239 (19) | 0.029 (2) | 0.0254 (19) | 0.0001 (16) | −0.0051 (16) | 0.0036 (16) |
C19 | 0.026 (2) | 0.031 (2) | 0.0239 (19) | −0.0012 (16) | −0.0008 (16) | 0.0018 (16) |
O6 | 0.0254 (14) | 0.0312 (16) | 0.0283 (15) | 0.0051 (12) | −0.0033 (12) | −0.0082 (12) |
C20 | 0.0220 (19) | 0.036 (2) | 0.029 (2) | 0.0019 (17) | −0.0038 (16) | −0.0089 (18) |
C21 | 0.034 (2) | 0.051 (3) | 0.033 (2) | 0.004 (2) | −0.0010 (19) | −0.016 (2) |
O7 | 0.0236 (14) | 0.0381 (17) | 0.0310 (16) | 0.0093 (13) | −0.0014 (12) | 0.0029 (13) |
C22 | 0.027 (2) | 0.061 (3) | 0.032 (2) | 0.015 (2) | 0.0008 (19) | 0.015 (2) |
C51 | 0.092 (5) | 0.094 (5) | 0.088 (6) | 0.040 (5) | 0.000 (5) | 0.013 (5) |
N52 | 0.059 (5) | 0.059 (5) | 0.047 (6) | 0.025 (3) | 0.003 (4) | 0.021 (4) |
C53 | 0.071 (5) | 0.079 (5) | 0.068 (5) | 0.029 (5) | −0.004 (5) | 0.013 (5) |
C54 | 0.081 (6) | 0.082 (6) | 0.095 (6) | 0.016 (5) | −0.015 (5) | 0.016 (5) |
C55 | 0.097 (6) | 0.093 (6) | 0.114 (6) | 0.007 (5) | −0.001 (6) | 0.009 (6) |
C56 | 0.089 (6) | 0.088 (6) | 0.107 (6) | 0.022 (5) | 0.008 (5) | 0.017 (5) |
C57 | 0.109 (7) | 0.124 (7) | 0.127 (7) | 0.040 (6) | −0.001 (6) | 0.030 (6) |
N0AA | 0.073 (8) | 0.111 (10) | 0.154 (13) | 0.043 (7) | −0.005 (9) | 0.093 (9) |
O1AA | 0.234 (15) | 0.260 (15) | 0.260 (15) | 0.026 (14) | −0.001 (13) | 0.021 (14) |
Geometric parameters (Å, º) top
N1—C6 | 1.391 (5) | S1—C13 | 1.763 (5) |
N1—C7 | 1.399 (5) | C14—C15 | 1.402 (6) |
N1—C11 | 1.474 (5) | C14—C19 | 1.376 (6) |
C1—C2 | 1.413 (6) | C15—C16 | 1.393 (6) |
C1—C8 | 1.381 (6) | C16—C17 | 1.405 (6) |
C1—N2 | 1.396 (5) | C16—O6 | 1.373 (5) |
C2—C3 | 1.385 (6) | C17—C18 | 1.375 (6) |
C3—C4 | 1.395 (6) | C17—O7 | 1.377 (5) |
C4—C5 | 1.383 (6) | C18—C19 | 1.405 (6) |
C5—C6 | 1.485 (6) | O6—C20 | 1.437 (5) |
C5—C8 | 1.391 (5) | C20—C21 | 1.508 (6) |
C6—O1 | 1.218 (5) | O7—C22 | 1.439 (5) |
C7—C8 | 1.483 (6) | C51—N52 | 1.3900 |
C7—O2 | 1.223 (5) | C51—C56 | 1.3900 |
C9—C10 | 1.490 (6) | C51—C57 | 1.140 (8) |
C9—N2 | 1.383 (5) | N52—C53 | 1.3900 |
C9—O3 | 1.222 (5) | C53—C54 | 1.3900 |
C11—C12 | 1.536 (5) | C54—C55 | 1.3900 |
C11—C14 | 1.531 (6) | C55—C56 | 1.3900 |
C12—S1 | 1.775 (4) | C57—N0AA | 1.429 (12) |
S1—O4 | 1.441 (3) | C57—O1AA | 1.247 (13) |
S1—O5 | 1.442 (3) | | |
| | | |
C6—N1—C7 | 110.9 (3) | O4—S1—C13 | 109.0 (2) |
C6—N1—C11 | 125.7 (3) | O5—S1—C12 | 109.28 (19) |
C7—N1—C11 | 123.1 (3) | O5—S1—C13 | 108.3 (2) |
C8—C1—C2 | 116.5 (4) | C13—S1—C12 | 102.2 (2) |
C8—C1—N2 | 118.6 (4) | C15—C14—C11 | 122.1 (4) |
N2—C1—C2 | 125.0 (4) | C19—C14—C11 | 118.0 (4) |
C3—C2—C1 | 120.3 (4) | C19—C14—C15 | 119.9 (4) |
C2—C3—C4 | 123.0 (4) | C16—C15—C14 | 120.5 (4) |
C5—C4—C3 | 116.0 (4) | C15—C16—C17 | 119.1 (4) |
C4—C5—C6 | 130.4 (4) | O6—C16—C15 | 123.9 (4) |
C4—C5—C8 | 121.7 (4) | O6—C16—C17 | 117.0 (4) |
C8—C5—C6 | 107.9 (3) | C18—C17—C16 | 120.2 (4) |
N1—C6—C5 | 106.7 (3) | C18—C17—O7 | 124.4 (4) |
O1—C6—N1 | 125.0 (4) | O7—C17—C16 | 115.4 (4) |
O1—C6—C5 | 128.3 (4) | C17—C18—C19 | 120.5 (4) |
N1—C7—C8 | 106.7 (3) | C14—C19—C18 | 119.9 (4) |
O2—C7—N1 | 125.0 (4) | C16—O6—C20 | 116.8 (3) |
O2—C7—C8 | 128.3 (4) | O6—C20—C21 | 108.6 (4) |
C1—C8—C5 | 122.4 (4) | C17—O7—C22 | 115.6 (3) |
C1—C8—C7 | 129.9 (4) | N52—C51—C56 | 120.0 |
C5—C8—C7 | 107.7 (3) | C57—C51—N52 | 110.4 (8) |
N2—C9—C10 | 114.0 (4) | C57—C51—C56 | 129.6 (8) |
O3—C9—C10 | 123.4 (4) | C51—N52—C53 | 120.0 |
O3—C9—N2 | 122.5 (4) | C54—C53—N52 | 120.0 |
C9—N2—C1 | 129.2 (4) | C53—C54—C55 | 120.0 |
N1—C11—C12 | 110.9 (3) | C56—C55—C54 | 120.0 |
N1—C11—C14 | 112.4 (3) | C55—C56—C51 | 120.0 |
C14—C11—C12 | 110.9 (3) | C51—C57—N0AA | 116.2 (12) |
C11—C12—S1 | 113.5 (3) | C51—C57—O1AA | 133.7 (19) |
O4—S1—C12 | 109.2 (2) | O1AA—C57—N0AA | 110.1 (15) |
O4—S1—O5 | 117.74 (19) | | |
Crystal data top
C22H24N2O7S·0.5(C3H6N2O) | Dx = 1.363 Mg m−3 |
Mr = 501.52 | Cu Kα radiation, λ = 1.54184 Å |
Tetragonal, P41212 | Cell parameters from 26834 reflections |
a = 12.85808 (14) Å | θ = 3.7–74.9° |
c = 29.5715 (4) Å | µ = 1.62 mm−1 |
V = 4889.07 (13) Å3 | T = 100 K |
Z = 8 | 0.47 × 0.24 × 0.12 mm |
F(000) = 2104 | |
Data collection top
SuperNova, Dual, Cu at zero, TitanS2 diffractometer | 5005 independent reflections |
Radiation source: sealed X-ray tube, SuperNova (Cu) X-ray Source | 4888 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.040 |
Detector resolution: 4.1685 pixels mm-1 | θmax = 75.0°, θmin = 3.8° |
ω scans | h = −15→15 |
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb 9 2015,16:26:32)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | k = −15→15 |
Tmin = 0.576, Tmax = 1.000 | l = −36→36 |
38007 measured reflections | |
Refinement top
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.1179P)2 + 6.0959P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.063 | (Δ/σ)max = 0.001 |
wR(F2) = 0.179 | Δρmax = 1.98 e Å−3 |
S = 1.05 | Δρmin = −0.96 e Å−3 |
5005 reflections | Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
335 parameters | Extinction coefficient: 0.0008 (3) |
66 restraints | Absolute structure: Flack x determined using 1984 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.006 (6) |
Hydrogen site location: mixed | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
N1 | 0.4649 (3) | 0.6546 (3) | 0.35360 (11) | 0.0222 (7) | |
C1 | 0.2893 (3) | 0.6339 (3) | 0.45127 (14) | 0.0230 (8) | |
C2 | 0.2053 (3) | 0.5645 (3) | 0.45526 (15) | 0.0262 (9) | |
H2 | 0.1649 | 0.5649 | 0.4813 | 0.031* | |
C3 | 0.1821 (4) | 0.4953 (4) | 0.42066 (16) | 0.0295 (10) | |
H3 | 0.1261 | 0.4503 | 0.4243 | 0.035* | |
C4 | 0.2395 (3) | 0.4904 (3) | 0.38033 (16) | 0.0272 (9) | |
H4 | 0.2231 | 0.4440 | 0.3573 | 0.033* | |
C5 | 0.3223 (3) | 0.5594 (3) | 0.37698 (14) | 0.0232 (8) | |
C6 | 0.3981 (4) | 0.5745 (3) | 0.33982 (14) | 0.0231 (8) | |
C7 | 0.4375 (3) | 0.6911 (3) | 0.39637 (13) | 0.0217 (8) | |
C8 | 0.3454 (3) | 0.6294 (3) | 0.41127 (14) | 0.0227 (8) | |
O1 | 0.4038 (3) | 0.5296 (2) | 0.30362 (10) | 0.0269 (7) | |
O2 | 0.4816 (3) | 0.7605 (2) | 0.41676 (10) | 0.0264 (7) | |
C9 | 0.2797 (4) | 0.7222 (4) | 0.52644 (14) | 0.0260 (9) | |
C10 | 0.3421 (4) | 0.7952 (4) | 0.55506 (15) | 0.0316 (10) | |
H10A | 0.4051 | 0.7615 | 0.5645 | 0.047* | |
H10B | 0.3024 | 0.8146 | 0.5812 | 0.047* | |
H10C | 0.3589 | 0.8562 | 0.5378 | 0.047* | |
N2 | 0.3211 (3) | 0.7050 (3) | 0.48438 (12) | 0.0247 (7) | |
H2A | 0.3737 | 0.7430 | 0.4774 | 0.030* | |
O3 | 0.2005 (3) | 0.6801 (3) | 0.53965 (10) | 0.0304 (7) | |
C11 | 0.5465 (3) | 0.7015 (3) | 0.32538 (14) | 0.0229 (8) | |
H11 | 0.5727 | 0.7622 | 0.3419 | 0.027* | |
C12 | 0.5021 (3) | 0.7416 (3) | 0.28060 (14) | 0.0245 (8) | |
H12A | 0.4736 | 0.6833 | 0.2639 | 0.029* | |
H12B | 0.5585 | 0.7706 | 0.2628 | 0.029* | |
S1 | 0.40402 (8) | 0.83733 (8) | 0.28678 (3) | 0.0248 (3) | |
O4 | 0.4454 (3) | 0.9244 (3) | 0.31175 (11) | 0.0326 (8) | |
O5 | 0.3107 (3) | 0.7890 (3) | 0.30390 (11) | 0.0314 (7) | |
C13 | 0.3825 (4) | 0.8757 (4) | 0.23034 (17) | 0.0366 (11) | |
H13A | 0.3582 | 0.8172 | 0.2132 | 0.055* | |
H13B | 0.4464 | 0.9008 | 0.2175 | 0.055* | |
H13C | 0.3313 | 0.9300 | 0.2296 | 0.055* | |
C14 | 0.6389 (3) | 0.6295 (3) | 0.31770 (14) | 0.0234 (8) | |
C15 | 0.6536 (3) | 0.5768 (3) | 0.27695 (14) | 0.0243 (8) | |
H15 | 0.6055 | 0.5848 | 0.2537 | 0.029* | |
C16 | 0.7397 (3) | 0.5122 (3) | 0.27064 (14) | 0.0253 (8) | |
C17 | 0.8124 (3) | 0.5017 (4) | 0.30584 (16) | 0.0271 (9) | |
C18 | 0.7982 (4) | 0.5543 (4) | 0.34599 (15) | 0.0285 (9) | |
H18 | 0.8467 | 0.5476 | 0.3691 | 0.034* | |
C19 | 0.7103 (4) | 0.6182 (4) | 0.35208 (15) | 0.0268 (9) | |
H19 | 0.7005 | 0.6528 | 0.3794 | 0.032* | |
O6 | 0.7586 (2) | 0.4563 (3) | 0.23211 (11) | 0.0294 (7) | |
C20 | 0.6804 (4) | 0.4614 (4) | 0.19724 (15) | 0.0299 (10) | |
H20A | 0.6767 | 0.5313 | 0.1850 | 0.036* | |
H20B | 0.6128 | 0.4437 | 0.2097 | 0.036* | |
C21 | 0.7092 (4) | 0.3856 (5) | 0.16050 (17) | 0.0387 (12) | |
H21A | 0.6541 | 0.3821 | 0.1387 | 0.058* | |
H21B | 0.7200 | 0.3180 | 0.1735 | 0.058* | |
H21C | 0.7720 | 0.4083 | 0.1460 | 0.058* | |
O7 | 0.8960 (3) | 0.4387 (3) | 0.29662 (11) | 0.0319 (8) | |
C22 | 0.9647 (4) | 0.4198 (5) | 0.33402 (18) | 0.0420 (13) | |
H22A | 1.0216 | 0.3771 | 0.3242 | 0.063* | |
H22B | 0.9274 | 0.3849 | 0.3577 | 0.063* | |
H22C | 0.9910 | 0.4848 | 0.3452 | 0.063* | |
N51 | 0.4527 (12) | 0.4626 (13) | 0.5050 (5) | 0.025 (2) | 0.5 |
H51 | 0.4092 | 0.4134 | 0.4995 | 0.030* | 0.5 |
C52 | 0.4582 (16) | 0.5225 (17) | 0.5452 (4) | 0.174 (12) | 0.5 |
H52 | 0.4153 | 0.5154 | 0.5704 | 0.208* | 0.5 |
C53 | 0.541 (2) | 0.595 (2) | 0.5404 (7) | 0.228 (14) | 0.5 |
H53 | 0.5613 | 0.6439 | 0.5618 | 0.273* | 0.5 |
N54 | 0.5862 (17) | 0.5801 (18) | 0.4971 (7) | 0.071 (3) | 0.5 |
C55 | 0.5318 (8) | 0.4982 (8) | 0.4752 (3) | 0.041 (2) | 0.5 |
H55 | 0.5456 | 0.4724 | 0.4465 | 0.049* | 0.5 |
O1W | 0.3451 (14) | 0.3451 (14) | 0.5000 | 0.228 (8) | |
H1WB | 0.2850 | 0.3517 | 0.4881 | 0.274* | 0.5 |
H1WA | 0.3471 | 0.2896 | 0.5119 | 0.274* | 0.5 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0229 (17) | 0.0236 (17) | 0.0201 (15) | −0.0006 (14) | −0.0005 (13) | −0.0010 (14) |
C1 | 0.023 (2) | 0.022 (2) | 0.0243 (19) | 0.0018 (15) | −0.0034 (16) | −0.0007 (15) |
C2 | 0.026 (2) | 0.025 (2) | 0.028 (2) | −0.0004 (16) | 0.0004 (16) | 0.0010 (16) |
C3 | 0.028 (2) | 0.024 (2) | 0.036 (2) | −0.0057 (18) | −0.0009 (18) | −0.0021 (18) |
C4 | 0.026 (2) | 0.024 (2) | 0.031 (2) | −0.0010 (17) | −0.0034 (17) | −0.0037 (17) |
C5 | 0.022 (2) | 0.0231 (19) | 0.0243 (18) | 0.0002 (16) | −0.0026 (16) | −0.0002 (16) |
C6 | 0.028 (2) | 0.0190 (19) | 0.0225 (19) | 0.0001 (16) | −0.0052 (16) | −0.0013 (15) |
C7 | 0.0218 (19) | 0.024 (2) | 0.0196 (17) | 0.0005 (15) | −0.0008 (15) | −0.0001 (15) |
C8 | 0.023 (2) | 0.0219 (19) | 0.0235 (19) | 0.0016 (15) | −0.0018 (16) | 0.0012 (15) |
O1 | 0.0320 (16) | 0.0256 (15) | 0.0232 (14) | 0.0006 (13) | −0.0021 (13) | −0.0049 (12) |
O2 | 0.0278 (16) | 0.0284 (16) | 0.0231 (13) | −0.0018 (12) | −0.0009 (12) | −0.0045 (12) |
C9 | 0.029 (2) | 0.028 (2) | 0.0214 (19) | 0.0019 (17) | 0.0002 (17) | −0.0001 (16) |
C10 | 0.032 (2) | 0.037 (3) | 0.026 (2) | −0.002 (2) | −0.0030 (19) | −0.0044 (19) |
N2 | 0.0237 (18) | 0.0291 (19) | 0.0215 (16) | −0.0044 (14) | 0.0023 (14) | −0.0034 (14) |
O3 | 0.0315 (17) | 0.0333 (17) | 0.0264 (14) | −0.0048 (14) | 0.0058 (13) | 0.0000 (13) |
C11 | 0.021 (2) | 0.023 (2) | 0.0242 (19) | −0.0007 (16) | 0.0006 (16) | −0.0016 (15) |
C12 | 0.028 (2) | 0.023 (2) | 0.0228 (18) | 0.0017 (15) | 0.0007 (16) | 0.0011 (16) |
S1 | 0.0257 (5) | 0.0254 (5) | 0.0233 (5) | 0.0038 (4) | 0.0010 (4) | 0.0012 (4) |
O4 | 0.0370 (18) | 0.0276 (16) | 0.0334 (16) | 0.0037 (13) | 0.0011 (14) | −0.0040 (13) |
O5 | 0.0240 (16) | 0.0375 (18) | 0.0327 (16) | 0.0021 (13) | 0.0046 (13) | 0.0012 (14) |
C13 | 0.038 (3) | 0.039 (3) | 0.033 (2) | 0.005 (2) | −0.002 (2) | 0.007 (2) |
C14 | 0.024 (2) | 0.0229 (19) | 0.0235 (19) | −0.0002 (16) | −0.0007 (16) | 0.0009 (15) |
C15 | 0.023 (2) | 0.025 (2) | 0.0248 (19) | 0.0004 (16) | −0.0028 (16) | −0.0010 (16) |
C16 | 0.026 (2) | 0.025 (2) | 0.0244 (19) | 0.0004 (16) | −0.0003 (16) | −0.0012 (16) |
C17 | 0.022 (2) | 0.029 (2) | 0.030 (2) | 0.0020 (17) | 0.0000 (17) | 0.0025 (17) |
C18 | 0.025 (2) | 0.032 (2) | 0.029 (2) | −0.0006 (17) | −0.0036 (17) | 0.0019 (18) |
C19 | 0.027 (2) | 0.031 (2) | 0.0229 (19) | −0.0007 (17) | −0.0014 (17) | 0.0004 (17) |
O6 | 0.0255 (16) | 0.0340 (17) | 0.0286 (15) | 0.0067 (13) | −0.0022 (12) | −0.0064 (13) |
C20 | 0.024 (2) | 0.036 (2) | 0.029 (2) | 0.0006 (18) | −0.0038 (17) | −0.0044 (19) |
C21 | 0.036 (3) | 0.046 (3) | 0.034 (2) | 0.003 (2) | −0.001 (2) | −0.012 (2) |
O7 | 0.0244 (16) | 0.0407 (19) | 0.0306 (16) | 0.0101 (14) | −0.0016 (13) | 0.0044 (14) |
C22 | 0.029 (2) | 0.062 (4) | 0.034 (2) | 0.016 (2) | −0.001 (2) | 0.014 (2) |
N51 | 0.027 (4) | 0.029 (4) | 0.018 (5) | 0.007 (3) | 0.002 (4) | −0.004 (4) |
C52 | 0.167 (13) | 0.173 (13) | 0.181 (13) | 0.006 (7) | 0.007 (7) | 0.021 (7) |
C53 | 0.230 (16) | 0.224 (15) | 0.228 (15) | 0.002 (7) | −0.004 (7) | −0.006 (7) |
N54 | 0.064 (6) | 0.070 (6) | 0.080 (5) | 0.007 (4) | −0.003 (5) | 0.013 (5) |
C55 | 0.041 (4) | 0.044 (5) | 0.037 (4) | 0.009 (4) | 0.004 (4) | 0.003 (4) |
O1W | 0.215 (9) | 0.215 (9) | 0.254 (13) | 0.099 (10) | −0.072 (7) | 0.072 (7) |
Geometric parameters (Å, º) top
N1—C6 | 1.401 (5) | S1—O4 | 1.443 (4) |
N1—C7 | 1.394 (5) | S1—O5 | 1.443 (3) |
N1—C11 | 1.471 (5) | S1—C13 | 1.762 (5) |
C1—C2 | 1.407 (6) | C14—C15 | 1.395 (6) |
C1—C8 | 1.387 (6) | C14—C19 | 1.377 (6) |
C1—N2 | 1.400 (5) | C15—C16 | 1.396 (6) |
C2—C3 | 1.388 (6) | C16—C17 | 1.406 (6) |
C3—C4 | 1.404 (7) | C16—O6 | 1.369 (5) |
C4—C5 | 1.389 (6) | C17—C18 | 1.379 (7) |
C5—C6 | 1.481 (6) | C17—O7 | 1.372 (5) |
C5—C8 | 1.388 (6) | C18—C19 | 1.408 (6) |
C6—O1 | 1.219 (5) | O6—C20 | 1.442 (5) |
C7—C8 | 1.491 (6) | C20—C21 | 1.506 (7) |
C7—O2 | 1.217 (5) | O7—C22 | 1.436 (6) |
C9—C10 | 1.497 (6) | N51—C52 | 1.4200 |
C9—N2 | 1.371 (5) | N51—C55 | 1.4200 |
C9—O3 | 1.217 (6) | C52—C53 | 1.4200 |
C11—C12 | 1.532 (6) | C53—N54 | 1.4200 |
C11—C14 | 1.523 (6) | N54—C55 | 1.4200 |
C12—S1 | 1.772 (4) | | |
| | | |
C6—N1—C11 | 125.0 (3) | C11—C12—S1 | 114.2 (3) |
C7—N1—C6 | 110.9 (3) | O4—S1—C12 | 109.2 (2) |
C7—N1—C11 | 123.8 (4) | O4—S1—C13 | 109.0 (2) |
C8—C1—C2 | 116.4 (4) | O5—S1—C12 | 109.2 (2) |
C8—C1—N2 | 118.2 (4) | O5—S1—O4 | 117.5 (2) |
N2—C1—C2 | 125.4 (4) | O5—S1—C13 | 108.8 (2) |
C3—C2—C1 | 120.6 (4) | C13—S1—C12 | 102.0 (2) |
C2—C3—C4 | 122.8 (4) | C15—C14—C11 | 122.0 (4) |
C5—C4—C3 | 115.8 (4) | C19—C14—C11 | 118.3 (4) |
C4—C5—C6 | 129.9 (4) | C19—C14—C15 | 119.7 (4) |
C8—C5—C4 | 121.7 (4) | C14—C15—C16 | 120.8 (4) |
C8—C5—C6 | 108.4 (4) | C15—C16—C17 | 119.0 (4) |
N1—C6—C5 | 106.5 (3) | O6—C16—C15 | 124.4 (4) |
O1—C6—N1 | 124.5 (4) | O6—C16—C17 | 116.6 (4) |
O1—C6—C5 | 129.0 (4) | C18—C17—C16 | 120.1 (4) |
N1—C7—C8 | 106.8 (3) | O7—C17—C16 | 115.5 (4) |
O2—C7—N1 | 125.3 (4) | O7—C17—C18 | 124.4 (4) |
O2—C7—C8 | 127.9 (4) | C17—C18—C19 | 120.2 (4) |
C1—C8—C5 | 122.6 (4) | C14—C19—C18 | 120.1 (4) |
C1—C8—C7 | 130.0 (4) | C16—O6—C20 | 116.6 (3) |
C5—C8—C7 | 107.4 (4) | O6—C20—C21 | 108.4 (4) |
N2—C9—C10 | 113.9 (4) | C17—O7—C22 | 115.4 (4) |
O3—C9—C10 | 123.1 (4) | C55—N51—C52 | 108.0 |
O3—C9—N2 | 123.0 (4) | C53—C52—N51 | 108.0 |
C9—N2—C1 | 128.8 (4) | N54—C53—C52 | 108.0 |
N1—C11—C12 | 111.3 (3) | C53—N54—C55 | 108.0 |
N1—C11—C14 | 113.1 (3) | N51—C55—N54 | 108.0 |
C14—C11—C12 | 111.5 (3) | | |
Crystal data top
C22H24N2O7S·0.5(C6H8O3) | Dx = 1.421 Mg m−3 |
Mr = 524.55 | Cu Kα radiation, λ = 1.54184 Å |
Tetragonal, P41212 | Cell parameters from 31560 reflections |
a = 12.88747 (7) Å | θ = 3.7–75.2° |
c = 29.5246 (3) Å | µ = 1.66 mm−1 |
V = 4903.65 (7) Å3 | T = 100 K |
Z = 8 | 0.26 × 0.16 × 0.12 mm |
F(000) = 2208 | |
Data collection top
SuperNova, Dual, Cu at zero, TitanS2 diffractometer | 5046 independent reflections |
Radiation source: sealed X-ray tube, SuperNova (Cu) X-ray Source | 5005 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.027 |
Detector resolution: 4.1685 pixels mm-1 | θmax = 75.4°, θmin = 3.7° |
ω scans | h = −16→15 |
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb 9 2015,16:26:32)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | k = −15→15 |
Tmin = 0.603, Tmax = 1.000 | l = −26→36 |
38399 measured reflections | |
Refinement top
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.1156P)2 + 5.1206P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.060 | (Δ/σ)max = 0.011 |
wR(F2) = 0.172 | Δρmax = 1.23 e Å−3 |
S = 1.06 | Δρmin = −0.97 e Å−3 |
5046 reflections | Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
359 parameters | Extinction coefficient: 0.0014 (3) |
114 restraints | Absolute structure: Flack x determined using 2039 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.003 (4) |
Hydrogen site location: mixed | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
N1 | 0.4651 (3) | 0.6554 (3) | 0.35354 (10) | 0.0218 (7) | |
C1 | 0.2906 (3) | 0.6352 (3) | 0.45141 (13) | 0.0219 (8) | |
C2 | 0.2072 (3) | 0.5641 (3) | 0.45568 (14) | 0.0277 (8) | |
H2 | 0.1674 | 0.5638 | 0.4819 | 0.033* | |
C3 | 0.1842 (3) | 0.4945 (3) | 0.42077 (15) | 0.0304 (9) | |
H3 | 0.1284 | 0.4494 | 0.4244 | 0.036* | |
C4 | 0.2415 (3) | 0.4900 (3) | 0.38079 (14) | 0.0276 (8) | |
H4 | 0.2262 | 0.4428 | 0.3579 | 0.033* | |
C5 | 0.3226 (3) | 0.5599 (3) | 0.37716 (13) | 0.0245 (8) | |
C6 | 0.3985 (3) | 0.5757 (3) | 0.33977 (13) | 0.0230 (8) | |
C7 | 0.4371 (3) | 0.6918 (3) | 0.39631 (12) | 0.0217 (7) | |
C8 | 0.3465 (3) | 0.6305 (3) | 0.41098 (13) | 0.0229 (8) | |
O1 | 0.4040 (2) | 0.5307 (2) | 0.30356 (10) | 0.0281 (6) | |
O2 | 0.4814 (2) | 0.7619 (2) | 0.41669 (9) | 0.0268 (6) | |
C9 | 0.2798 (3) | 0.7227 (3) | 0.52673 (13) | 0.0253 (8) | |
C10 | 0.3417 (4) | 0.7957 (4) | 0.55544 (14) | 0.0297 (9) | |
H10A | 0.4006 | 0.7598 | 0.5678 | 0.045* | |
H10B | 0.2992 | 0.8212 | 0.5797 | 0.045* | |
H10C | 0.3651 | 0.8528 | 0.5373 | 0.045* | |
N2 | 0.3218 (3) | 0.7058 (3) | 0.48444 (11) | 0.0241 (7) | |
H2A | 0.3742 | 0.7439 | 0.4775 | 0.029* | |
O3 | 0.2001 (2) | 0.6807 (3) | 0.53947 (10) | 0.0310 (7) | |
C11 | 0.5465 (3) | 0.7022 (3) | 0.32520 (13) | 0.0238 (8) | |
H11 | 0.5729 | 0.7627 | 0.3417 | 0.029* | |
C12 | 0.5021 (3) | 0.7425 (3) | 0.28043 (13) | 0.0251 (8) | |
H12A | 0.4737 | 0.6843 | 0.2636 | 0.030* | |
H12B | 0.5582 | 0.7715 | 0.2626 | 0.030* | |
S1 | 0.40433 (8) | 0.83764 (8) | 0.28677 (3) | 0.0253 (3) | |
O4 | 0.4448 (3) | 0.9240 (2) | 0.31234 (11) | 0.0341 (7) | |
O5 | 0.3110 (2) | 0.7888 (3) | 0.30332 (11) | 0.0312 (7) | |
C13 | 0.3832 (4) | 0.8776 (4) | 0.23061 (16) | 0.0385 (11) | |
H13A | 0.3620 | 0.8191 | 0.2127 | 0.058* | |
H13B | 0.4461 | 0.9060 | 0.2185 | 0.058* | |
H13C | 0.3298 | 0.9295 | 0.2300 | 0.058* | |
C14 | 0.6381 (3) | 0.6304 (3) | 0.31741 (14) | 0.0245 (8) | |
C15 | 0.6526 (3) | 0.5767 (3) | 0.27641 (13) | 0.0245 (8) | |
H15 | 0.6044 | 0.5843 | 0.2532 | 0.029* | |
C16 | 0.7377 (3) | 0.5126 (3) | 0.27010 (14) | 0.0255 (8) | |
C17 | 0.8116 (3) | 0.5025 (3) | 0.30478 (15) | 0.0283 (9) | |
C18 | 0.7973 (3) | 0.5550 (4) | 0.34527 (15) | 0.0299 (9) | |
H18 | 0.8456 | 0.5479 | 0.3685 | 0.036* | |
C19 | 0.7104 (3) | 0.6188 (3) | 0.35144 (14) | 0.0286 (9) | |
H19 | 0.7014 | 0.6537 | 0.3787 | 0.034* | |
O6 | 0.7563 (2) | 0.4572 (2) | 0.23120 (10) | 0.0303 (7) | |
C20 | 0.6791 (3) | 0.4631 (4) | 0.19619 (15) | 0.0315 (9) | |
H20A | 0.6747 | 0.5334 | 0.1846 | 0.038* | |
H20B | 0.6117 | 0.4439 | 0.2082 | 0.038* | |
C21 | 0.7095 (4) | 0.3899 (5) | 0.15889 (18) | 0.0459 (13) | |
H21A | 0.6573 | 0.3906 | 0.1357 | 0.069* | |
H21B | 0.7162 | 0.3210 | 0.1709 | 0.069* | |
H21C | 0.7747 | 0.4114 | 0.1462 | 0.069* | |
O7 | 0.8942 (3) | 0.4394 (3) | 0.29568 (11) | 0.0370 (8) | |
C22 | 0.9622 (4) | 0.4177 (5) | 0.33275 (17) | 0.0474 (14) | |
H22A | 1.0157 | 0.3709 | 0.3230 | 0.071* | |
H22B | 0.9235 | 0.3865 | 0.3570 | 0.071* | |
H22C | 0.9932 | 0.4811 | 0.3432 | 0.071* | |
C51 | 0.4508 (8) | 0.4438 (8) | 0.4947 (3) | 0.047 (2) | 0.5 |
C52 | 0.4253 (8) | 0.4741 (8) | 0.5385 (3) | 0.086 (4) | 0.5 |
H52 | 0.3719 | 0.4407 | 0.5539 | 0.103* | 0.5 |
C53 | 0.4796 (8) | 0.5541 (8) | 0.5593 (2) | 0.065 (3) | 0.5 |
H53 | 0.4625 | 0.5744 | 0.5886 | 0.077* | 0.5 |
C54 | 0.5595 (9) | 0.6039 (9) | 0.5363 (3) | 0.107 (4) | 0.5 |
C55 | 0.5850 (8) | 0.5737 (9) | 0.4925 (3) | 0.069 (3) | 0.5 |
H55 | 0.6384 | 0.6070 | 0.4771 | 0.083* | 0.5 |
C56 | 0.5307 (7) | 0.4936 (7) | 0.4717 (2) | 0.062 (3) | 0.5 |
H56 | 0.5478 | 0.4733 | 0.4424 | 0.074* | 0.5 |
O51 | 0.4033 (12) | 0.3598 (11) | 0.4762 (5) | 0.162 (7) | 0.5 |
H51 | 0.3603 | 0.3368 | 0.4940 | 0.242* | 0.5 |
O54 | 0.5925 (18) | 0.6980 (14) | 0.5521 (6) | 0.221 (10) | 0.5 |
H54 | 0.6515 | 0.7095 | 0.5428 | 0.331* | 0.5 |
O1W | 0.2851 (15) | 0.2851 (15) | 0.5000 | 0.248 (9) | |
H1WA | 0.2211 | 0.2832 | 0.4939 | 0.298* | 0.5 |
H1WB | 0.2925 | 0.2118 | 0.5062 | 0.298* | 0.5 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0250 (16) | 0.0216 (15) | 0.0188 (14) | −0.0015 (13) | −0.0032 (12) | −0.0022 (12) |
C1 | 0.0240 (18) | 0.0206 (17) | 0.0211 (17) | 0.0020 (14) | −0.0033 (14) | −0.0012 (14) |
C2 | 0.027 (2) | 0.027 (2) | 0.028 (2) | −0.0022 (16) | 0.0004 (16) | 0.0003 (16) |
C3 | 0.031 (2) | 0.027 (2) | 0.034 (2) | −0.0051 (17) | 0.0004 (17) | −0.0033 (16) |
C4 | 0.031 (2) | 0.0229 (18) | 0.029 (2) | −0.0014 (16) | −0.0014 (16) | −0.0052 (16) |
C5 | 0.030 (2) | 0.0220 (17) | 0.0219 (17) | 0.0010 (15) | −0.0029 (15) | −0.0017 (14) |
C6 | 0.0270 (18) | 0.0194 (17) | 0.0225 (18) | 0.0001 (15) | −0.0045 (15) | −0.0011 (14) |
C7 | 0.0236 (18) | 0.0220 (17) | 0.0194 (16) | 0.0005 (14) | −0.0015 (14) | 0.0006 (14) |
C8 | 0.0245 (18) | 0.0230 (18) | 0.0211 (18) | 0.0003 (14) | −0.0027 (15) | 0.0011 (14) |
O1 | 0.0366 (16) | 0.0257 (14) | 0.0221 (13) | −0.0004 (12) | −0.0029 (12) | −0.0054 (11) |
O2 | 0.0294 (14) | 0.0301 (15) | 0.0209 (13) | −0.0050 (11) | −0.0022 (11) | −0.0060 (11) |
C9 | 0.029 (2) | 0.0257 (19) | 0.0208 (18) | 0.0028 (15) | −0.0012 (15) | −0.0008 (15) |
C10 | 0.031 (2) | 0.036 (2) | 0.0222 (18) | −0.0010 (17) | −0.0004 (16) | −0.0035 (17) |
N2 | 0.0254 (16) | 0.0278 (17) | 0.0191 (14) | −0.0045 (13) | 0.0024 (13) | −0.0021 (13) |
O3 | 0.0322 (15) | 0.0351 (16) | 0.0256 (14) | −0.0042 (13) | 0.0046 (12) | −0.0005 (12) |
C11 | 0.0236 (19) | 0.0264 (19) | 0.0215 (17) | −0.0029 (15) | 0.0000 (15) | −0.0012 (14) |
C12 | 0.030 (2) | 0.0254 (18) | 0.0195 (17) | 0.0016 (15) | 0.0009 (15) | 0.0016 (15) |
S1 | 0.0268 (5) | 0.0264 (5) | 0.0227 (4) | 0.0035 (4) | 0.0001 (4) | 0.0020 (4) |
O4 | 0.0375 (17) | 0.0282 (15) | 0.0367 (16) | 0.0035 (13) | −0.0004 (13) | −0.0065 (13) |
O5 | 0.0259 (15) | 0.0344 (16) | 0.0332 (15) | 0.0011 (12) | 0.0031 (12) | 0.0039 (13) |
C13 | 0.041 (3) | 0.044 (3) | 0.030 (2) | 0.007 (2) | −0.0024 (19) | 0.0119 (19) |
C14 | 0.027 (2) | 0.0252 (18) | 0.0214 (18) | 0.0005 (16) | −0.0020 (15) | 0.0009 (14) |
C15 | 0.0247 (19) | 0.0272 (19) | 0.0216 (18) | 0.0005 (15) | −0.0023 (15) | −0.0010 (15) |
C16 | 0.0280 (19) | 0.0239 (19) | 0.0246 (18) | −0.0002 (15) | 0.0004 (15) | −0.0015 (15) |
C17 | 0.0229 (19) | 0.032 (2) | 0.030 (2) | 0.0007 (16) | 0.0019 (16) | 0.0054 (16) |
C18 | 0.027 (2) | 0.033 (2) | 0.030 (2) | −0.0015 (16) | −0.0062 (17) | 0.0044 (17) |
C19 | 0.030 (2) | 0.034 (2) | 0.0217 (18) | −0.0004 (17) | −0.0045 (16) | 0.0007 (16) |
O6 | 0.0300 (15) | 0.0326 (16) | 0.0284 (14) | 0.0047 (12) | 0.0014 (12) | −0.0039 (12) |
C20 | 0.0239 (19) | 0.038 (2) | 0.032 (2) | 0.0020 (17) | −0.0002 (16) | −0.0077 (18) |
C21 | 0.039 (3) | 0.058 (3) | 0.041 (3) | 0.005 (2) | 0.000 (2) | −0.021 (2) |
O7 | 0.0298 (16) | 0.0481 (19) | 0.0331 (16) | 0.0134 (14) | 0.0028 (13) | 0.0087 (14) |
C22 | 0.033 (2) | 0.072 (4) | 0.037 (2) | 0.023 (3) | 0.005 (2) | 0.022 (3) |
C51 | 0.045 (5) | 0.061 (6) | 0.034 (5) | 0.028 (4) | 0.015 (4) | 0.025 (4) |
C52 | 0.080 (6) | 0.086 (7) | 0.093 (7) | 0.017 (6) | −0.006 (6) | 0.013 (6) |
C53 | 0.063 (6) | 0.061 (6) | 0.070 (6) | 0.011 (5) | −0.006 (5) | 0.018 (5) |
C54 | 0.090 (7) | 0.114 (7) | 0.117 (7) | 0.009 (6) | 0.015 (6) | 0.037 (7) |
C55 | 0.045 (5) | 0.079 (6) | 0.084 (7) | 0.016 (4) | 0.018 (5) | 0.043 (6) |
C56 | 0.045 (5) | 0.070 (6) | 0.070 (6) | 0.021 (5) | 0.008 (5) | 0.032 (5) |
O51 | 0.160 (12) | 0.154 (11) | 0.170 (12) | 0.046 (11) | −0.008 (11) | 0.053 (10) |
O54 | 0.214 (16) | 0.238 (17) | 0.210 (16) | 0.025 (15) | 0.016 (14) | −0.009 (14) |
O1W | 0.246 (10) | 0.246 (10) | 0.253 (15) | 0.087 (13) | −0.037 (9) | 0.037 (9) |
Geometric parameters (Å, º) top
N1—C6 | 1.399 (5) | S1—O5 | 1.443 (3) |
N1—C7 | 1.395 (5) | S1—C13 | 1.757 (5) |
N1—C11 | 1.472 (5) | C14—C15 | 1.407 (6) |
C1—C2 | 1.418 (6) | C14—C19 | 1.378 (6) |
C1—C8 | 1.396 (6) | C15—C16 | 1.385 (6) |
C1—N2 | 1.393 (5) | C16—C17 | 1.405 (6) |
C2—C3 | 1.398 (6) | C16—O6 | 1.374 (5) |
C3—C4 | 1.394 (6) | C17—C18 | 1.386 (6) |
C4—C5 | 1.385 (6) | C17—O7 | 1.365 (5) |
C5—C6 | 1.488 (6) | C18—C19 | 1.402 (6) |
C5—C8 | 1.386 (5) | O6—C20 | 1.437 (5) |
C6—O1 | 1.218 (5) | C20—C21 | 1.502 (6) |
C7—C8 | 1.474 (5) | O7—C22 | 1.430 (6) |
C7—O2 | 1.227 (5) | C51—C52 | 1.3900 |
C9—C10 | 1.496 (6) | C51—C56 | 1.3900 |
C9—N2 | 1.378 (5) | C51—O51 | 1.359 (5) |
C9—O3 | 1.221 (5) | C52—C53 | 1.3900 |
C11—C12 | 1.531 (5) | C53—C54 | 1.3900 |
C11—C14 | 1.518 (6) | C54—C55 | 1.3900 |
C12—S1 | 1.769 (4) | C54—O54 | 1.367 (6) |
S1—O4 | 1.443 (3) | C55—C56 | 1.3900 |
| | | |
C6—N1—C11 | 125.0 (3) | O4—S1—O5 | 117.4 (2) |
C7—N1—C6 | 110.6 (3) | O4—S1—C13 | 108.9 (2) |
C7—N1—C11 | 124.2 (3) | O5—S1—C12 | 109.11 (19) |
C8—C1—C2 | 116.1 (4) | O5—S1—C13 | 108.5 (2) |
N2—C1—C2 | 125.3 (4) | C13—S1—C12 | 102.4 (2) |
N2—C1—C8 | 118.5 (4) | C15—C14—C11 | 122.3 (4) |
C3—C2—C1 | 120.7 (4) | C19—C14—C11 | 118.8 (4) |
C4—C3—C2 | 122.6 (4) | C19—C14—C15 | 119.0 (4) |
C5—C4—C3 | 116.0 (4) | C16—C15—C14 | 120.9 (4) |
C4—C5—C6 | 129.9 (4) | C15—C16—C17 | 119.6 (4) |
C4—C5—C8 | 122.7 (4) | O6—C16—C15 | 124.1 (4) |
C8—C5—C6 | 107.4 (4) | O6—C16—C17 | 116.3 (4) |
N1—C6—C5 | 106.7 (3) | C18—C17—C16 | 119.5 (4) |
O1—C6—N1 | 124.6 (4) | O7—C17—C16 | 116.1 (4) |
O1—C6—C5 | 128.7 (4) | O7—C17—C18 | 124.3 (4) |
N1—C7—C8 | 106.9 (3) | C17—C18—C19 | 120.3 (4) |
O2—C7—N1 | 124.8 (4) | C14—C19—C18 | 120.6 (4) |
O2—C7—C8 | 128.3 (3) | C16—O6—C20 | 116.9 (3) |
C1—C8—C7 | 129.6 (4) | O6—C20—C21 | 108.2 (4) |
C5—C8—C1 | 122.0 (4) | C17—O7—C22 | 116.3 (4) |
C5—C8—C7 | 108.4 (3) | C52—C51—C56 | 120.0 |
N2—C9—C10 | 113.8 (4) | O51—C51—C52 | 119.4 (4) |
O3—C9—C10 | 123.6 (4) | O51—C51—C56 | 120.3 (4) |
O3—C9—N2 | 122.6 (4) | C51—C52—C53 | 120.0 |
C9—N2—C1 | 128.7 (4) | C54—C53—C52 | 120.0 |
N1—C11—C12 | 111.3 (3) | C55—C54—C53 | 120.0 |
N1—C11—C14 | 113.0 (3) | O54—C54—C53 | 118.3 (5) |
C14—C11—C12 | 111.5 (3) | O54—C54—C55 | 119.5 (5) |
C11—C12—S1 | 114.2 (3) | C54—C55—C56 | 120.0 |
O4—S1—C12 | 109.5 (2) | C55—C56—C51 | 120.0 |