Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100017972/sk1435sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100017972/sk1435Isup2.hkl |
CCDC reference: 162568
A solution of 1,4-bis(2'-formylphenyl)-1,4-dioxabutane (10 mmol) in ethanol (150 ml) was slowly dripped into a refluxing solution of thiocarbohydrazide (10 mmol) in aqueous ethanol (100 ml), followed by the addition of concentrated hydrochloric acid (0.25 ml). The reaction mixture was refluxed for 10 h with stirring and cooled to room temperature. The yellow precipitate powder of (I) was filtered and thoroughly washed with water and ethanol, and then air dried. A crystal suitable for X-ray diffraction was obtained by evaporation from a benzene-pyridine (1:1) solution.
After checking their presence in the difference map, all H atoms were geometrically fixed and allowed to ride on the atoms to which they were attached, with Uiso = 1.2Ueq for the parent atoms, and with C—H 0.93–0.97 Å and N—H 0.86 Å. Query. The ratio of the major to the minor component of the disordered dioxabutane group is 0.56:0.44. The bond lengths of the disordered group were restrained to be the same as those of the non-disordered dioxabutane group.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 1990).
Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms and the pyridine solvate molecules have been omitted for clarity. |
C34H32N8O4S2·3C5H5N | F(000) = 1928 |
Mr = 918.10 | Dx = 1.278 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.1752 (2) Å | Cell parameters from 5918 reflections |
b = 22.2029 (1) Å | θ = 2.8–33.1° |
c = 19.8479 (4) Å | µ = 0.17 mm−1 |
β = 117.168 (1)° | T = 293 K |
V = 4773.42 (13) Å3 | Block, yellow |
Z = 4 | 0.37 × 0.33 × 0.28 mm |
Siemens SMART CCD area-detector diffractometer | 10907 independent reflections |
Radiation source: fine-focus sealed tube | 5918 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
Detector resolution: 8.33 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ω scans | h = −14→15 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −28→23 |
Tmin = 0.941, Tmax = 0.955 | l = −25→23 |
30445 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.068 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.166 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.046P)2 + 2.8579P] where P = (Fo2 + 2Fc2)/3 |
10907 reflections | (Δ/σ)max < 0.001 |
593 parameters | Δρmax = 0.46 e Å−3 |
9 restraints | Δρmin = −0.49 e Å−3 |
C34H32N8O4S2·3C5H5N | V = 4773.42 (13) Å3 |
Mr = 918.10 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.1752 (2) Å | µ = 0.17 mm−1 |
b = 22.2029 (1) Å | T = 293 K |
c = 19.8479 (4) Å | 0.37 × 0.33 × 0.28 mm |
β = 117.168 (1)° |
Siemens SMART CCD area-detector diffractometer | 10907 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 5918 reflections with I > 2σ(I) |
Tmin = 0.941, Tmax = 0.955 | Rint = 0.043 |
30445 measured reflections |
R[F2 > 2σ(F2)] = 0.068 | 9 restraints |
wR(F2) = 0.166 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.46 e Å−3 |
10907 reflections | Δρmin = −0.49 e Å−3 |
593 parameters |
Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0,88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Coverage of the unique set is over 99% complete. Crystal decay was monitored by repeating thirty initial frames at the end of data collection and analysing the duplicate reflections and was found to be negligible. The hydrogen atom positions were fixed geometrically at calculated distances. The final difference Fourier map was found to be featureless. Table 2. Cg1 is the centroid of C20—C25 ring Cg2 is the centroid of C28—C33 ring Cg3 is the centroid of N10, C40—C44 ring Cg4 is the centroid of C11—C16 ring |
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. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the duplicate reflections, and was found to be negligible. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 0.04919 (7) | 0.67961 (4) | 0.17047 (4) | 0.0621 (2) | |
S2 | 0.38483 (9) | 0.58139 (4) | 0.14943 (5) | 0.0730 (3) | |
O1 | −0.0180 (2) | 0.43136 (10) | 0.36967 (13) | 0.0728 (6) | |
O2 | 0.01687 (18) | 0.39170 (10) | 0.24825 (12) | 0.0658 (6) | |
O3 | 0.7069 (3) | 0.70860 (14) | 0.52167 (18) | 0.1176 (11) | |
O4A | 0.5806 (7) | 0.7983 (6) | 0.4807 (5) | 0.097 (3) | 0.44 |
O4B | 0.5355 (6) | 0.8100 (5) | 0.4816 (3) | 0.097 (3) | 0.56 |
N1 | 0.0782 (2) | 0.60680 (11) | 0.28071 (13) | 0.0532 (6) | |
H1A | 0.0177 | 0.5870 | 0.2465 | 0.064* | |
N2 | 0.1309 (2) | 0.58616 (11) | 0.35436 (13) | 0.0533 (6) | |
N3 | 0.2141 (2) | 0.68502 (10) | 0.31799 (13) | 0.0519 (6) | |
H3A | 0.2409 | 0.6722 | 0.3637 | 0.062* | |
N4 | 0.2681 (2) | 0.73424 (11) | 0.30285 (13) | 0.0505 (6) | |
N5 | 0.2240 (2) | 0.50083 (11) | 0.19091 (13) | 0.0509 (6) | |
N6 | 0.3069 (2) | 0.53812 (11) | 0.24661 (13) | 0.0527 (6) | |
H6A | 0.3119 | 0.5375 | 0.2913 | 0.063* | |
N7 | 0.4556 (2) | 0.60969 (11) | 0.29171 (13) | 0.0567 (6) | |
H7A | 0.4979 | 0.6382 | 0.2855 | 0.068* | |
N8 | 0.4655 (2) | 0.59938 (11) | 0.36251 (13) | 0.0520 (6) | |
C1 | 0.1186 (2) | 0.65706 (13) | 0.26042 (15) | 0.0460 (6) | |
C2 | 0.0815 (3) | 0.53824 (14) | 0.36357 (17) | 0.0548 (7) | |
H2B | 0.0166 | 0.5212 | 0.3213 | 0.066* | |
C3 | 0.1212 (3) | 0.50868 (14) | 0.43656 (17) | 0.0547 (7) | |
C4 | 0.2079 (3) | 0.53332 (17) | 0.50498 (19) | 0.0728 (9) | |
H4B | 0.2430 | 0.5706 | 0.5053 | 0.087* | |
C5 | 0.2419 (4) | 0.5028 (2) | 0.5721 (2) | 0.0859 (11) | |
H5B | 0.2988 | 0.5198 | 0.6175 | 0.103* | |
C6 | 0.1917 (4) | 0.4473 (2) | 0.5720 (2) | 0.0848 (11) | |
H6B | 0.2160 | 0.4266 | 0.6174 | 0.102* | |
C7 | 0.1059 (3) | 0.42210 (17) | 0.5054 (2) | 0.0775 (10) | |
H7B | 0.0717 | 0.3847 | 0.5058 | 0.093* | |
C8 | 0.0706 (3) | 0.45245 (15) | 0.43812 (18) | 0.0593 (8) | |
C9 | −0.0163 (3) | 0.36919 (15) | 0.3533 (2) | 0.0730 (10) | |
H9A | −0.0662 | 0.3466 | 0.3710 | 0.088* | |
H9B | 0.0676 | 0.3539 | 0.3787 | 0.088* | |
C10 | −0.0664 (3) | 0.36210 (15) | 0.27001 (19) | 0.0682 (9) | |
H10A | −0.0729 | 0.3197 | 0.2567 | 0.082* | |
H10B | −0.1478 | 0.3801 | 0.2442 | 0.082* | |
C11 | −0.0108 (3) | 0.39220 (13) | 0.17310 (17) | 0.0533 (7) | |
C12 | −0.1066 (3) | 0.35894 (14) | 0.1176 (2) | 0.0648 (9) | |
H12A | −0.1571 | 0.3352 | 0.1305 | 0.078* | |
C13 | −0.1262 (3) | 0.36126 (16) | 0.0441 (2) | 0.0763 (10) | |
H13A | −0.1911 | 0.3395 | 0.0073 | 0.092* | |
C14 | −0.0522 (3) | 0.39498 (17) | 0.0234 (2) | 0.0768 (10) | |
H14A | −0.0648 | 0.3950 | −0.0265 | 0.092* | |
C15 | 0.0419 (3) | 0.42911 (15) | 0.07811 (17) | 0.0640 (8) | |
H15A | 0.0920 | 0.4525 | 0.0644 | 0.077* | |
C16 | 0.0625 (2) | 0.42887 (12) | 0.15315 (16) | 0.0487 (7) | |
C17 | 0.1554 (2) | 0.46877 (12) | 0.20940 (16) | 0.0481 (7) | |
H17A | 0.1640 | 0.4706 | 0.2584 | 0.058* | |
C18 | 0.3800 (3) | 0.57547 (13) | 0.23124 (16) | 0.0500 (7) | |
C19 | 0.5452 (3) | 0.63225 (14) | 0.41509 (16) | 0.0563 (8) | |
H19A | 0.5875 | 0.6613 | 0.4023 | 0.068* | |
C20 | 0.5720 (3) | 0.62590 (17) | 0.49349 (18) | 0.0644 (9) | |
C21 | 0.5175 (4) | 0.5820 (2) | 0.5174 (2) | 0.1002 (11) | |
H21A | 0.4610 | 0.5559 | 0.4819 | 0.120* | |
C22 | 0.5449 (4) | 0.5756 (2) | 0.5937 (3) | 0.1068 (15) | |
H22A | 0.5082 | 0.5453 | 0.6089 | 0.128* | |
C23 | 0.6269 (4) | 0.6150 (3) | 0.6454 (2) | 0.1002 (11) | |
H23A | 0.6449 | 0.6115 | 0.6961 | 0.120* | |
C24 | 0.6819 (3) | 0.6585 (2) | 0.6244 (2) | 0.1011 (11) | |
H24A | 0.7385 | 0.6840 | 0.6609 | 0.121* | |
C25 | 0.6549 (3) | 0.6660 (2) | 0.5481 (2) | 0.1011 (11) | |
C26A | 0.7342 (9) | 0.7540 (3) | 0.5787 (4) | 0.092 (2) | 0.44 |
H26A | 0.8189 | 0.7523 | 0.6181 | 0.110* | 0.44 |
H26B | 0.6779 | 0.7532 | 0.6009 | 0.110* | 0.44 |
C27A | 0.7115 (8) | 0.8045 (5) | 0.5273 (5) | 0.092 (2) | 0.44 |
H27A | 0.7323 | 0.8426 | 0.5541 | 0.110* | 0.44 |
H27B | 0.7567 | 0.8004 | 0.4980 | 0.110* | 0.44 |
C26B | 0.7447 (7) | 0.7705 (3) | 0.5477 (5) | 0.0931 (18) | 0.56 |
H26C | 0.8150 | 0.7690 | 0.5976 | 0.112* | 0.56 |
H26D | 0.7720 | 0.7895 | 0.5139 | 0.112* | 0.56 |
C27B | 0.6494 (6) | 0.8085 (3) | 0.5517 (4) | 0.0931 (18) | 0.56 |
H27C | 0.6320 | 0.7937 | 0.5918 | 0.112* | 0.56 |
H27D | 0.6809 | 0.8492 | 0.5648 | 0.112* | 0.56 |
C28 | 0.5314 (3) | 0.83009 (15) | 0.41413 (19) | 0.0717 (9) | |
C29 | 0.5997 (4) | 0.87649 (18) | 0.4058 (3) | 0.0921 (13) | |
H29A | 0.6679 | 0.8913 | 0.4480 | 0.111* | |
C30 | 0.5680 (4) | 0.90064 (19) | 0.3365 (3) | 0.0947 (14) | |
H30A | 0.6148 | 0.9318 | 0.3316 | 0.114* | |
C31 | 0.4671 (4) | 0.87926 (19) | 0.2734 (3) | 0.0898 (12) | |
H31A | 0.4457 | 0.8959 | 0.2260 | 0.108* | |
C32 | 0.3980 (3) | 0.83291 (15) | 0.28104 (19) | 0.0663 (9) | |
H32A | 0.3293 | 0.8188 | 0.2385 | 0.080* | |
C33 | 0.4291 (3) | 0.80737 (13) | 0.35059 (17) | 0.0506 (7) | |
C34 | 0.3612 (3) | 0.75629 (13) | 0.35959 (16) | 0.0514 (7) | |
H34A | 0.3863 | 0.7396 | 0.4074 | 0.062* | |
N9 | 0.8541 (2) | 0.54179 (12) | 0.16849 (15) | 0.0652 (7) | |
C35 | 0.7659 (4) | 0.51624 (18) | 0.1801 (2) | 0.0834 (11) | |
H35A | 0.7690 | 0.5199 | 0.2276 | 0.100* | |
C36 | 0.6686 (4) | 0.4840 (2) | 0.1242 (3) | 0.1008 (14) | |
H36A | 0.6072 | 0.4671 | 0.1337 | 0.121* | |
C37 | 0.6665 (4) | 0.4781 (2) | 0.0549 (3) | 0.0974 (14) | |
H37A | 0.6037 | 0.4562 | 0.0167 | 0.117* | |
C38 | 0.7556 (4) | 0.50391 (16) | 0.0422 (2) | 0.0792 (11) | |
H38A | 0.7553 | 0.5005 | −0.0046 | 0.095* | |
C39 | 0.8458 (3) | 0.53512 (15) | 0.0999 (2) | 0.0680 (9) | |
H39A | 0.9064 | 0.5532 | 0.0905 | 0.082* | |
N10 | 0.2669 (3) | 0.69707 (14) | 0.48367 (16) | 0.0742 (8) | |
C40 | 0.3624 (4) | 0.71843 (18) | 0.5426 (2) | 0.0803 (11) | |
H40A | 0.4392 | 0.7155 | 0.5435 | 0.096* | |
C41 | 0.3565 (4) | 0.74533 (19) | 0.6041 (2) | 0.0882 (12) | |
H41A | 0.4278 | 0.7598 | 0.6445 | 0.106* | |
C42 | 0.2473 (5) | 0.7501 (2) | 0.6045 (2) | 0.0892 (12) | |
H42A | 0.2407 | 0.7681 | 0.6448 | 0.107* | |
C43 | 0.1442 (4) | 0.72752 (18) | 0.5428 (3) | 0.0891 (12) | |
H43A | 0.0666 | 0.7300 | 0.5409 | 0.107* | |
C44 | 0.1583 (4) | 0.70119 (17) | 0.4842 (2) | 0.0802 (10) | |
H44A | 0.0889 | 0.6857 | 0.4433 | 0.096* | |
N11 | 0.6473 (2) | 0.69264 (13) | 0.28693 (16) | 0.0697 (8) | |
C45 | 0.7047 (4) | 0.74042 (18) | 0.3280 (2) | 0.0863 (12) | |
H45A | 0.6680 | 0.7609 | 0.3534 | 0.104* | |
C46 | 0.8160 (4) | 0.76124 (19) | 0.3349 (2) | 0.0896 (12) | |
H46A | 0.8537 | 0.7949 | 0.3644 | 0.108* | |
C47 | 0.8693 (3) | 0.7315 (2) | 0.2978 (2) | 0.0830 (11) | |
H47A | 0.9449 | 0.7441 | 0.3018 | 0.100* | |
C48 | 0.8110 (3) | 0.68309 (18) | 0.2547 (2) | 0.0727 (10) | |
H48A | 0.8452 | 0.6624 | 0.2281 | 0.087* | |
C49 | 0.7014 (3) | 0.66525 (16) | 0.25110 (18) | 0.0651 (9) | |
H49A | 0.6625 | 0.6318 | 0.2216 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0543 (4) | 0.0684 (5) | 0.0546 (4) | −0.0071 (4) | 0.0171 (4) | 0.0092 (4) |
S2 | 0.0896 (6) | 0.0779 (6) | 0.0559 (5) | −0.0260 (5) | 0.0371 (5) | −0.0124 (4) |
O1 | 0.0793 (15) | 0.0570 (15) | 0.0708 (15) | −0.0063 (12) | 0.0245 (13) | 0.0026 (12) |
O2 | 0.0535 (12) | 0.0740 (15) | 0.0630 (13) | −0.0230 (11) | 0.0207 (10) | −0.0023 (11) |
O3 | 0.0799 (19) | 0.129 (3) | 0.129 (2) | −0.0426 (18) | 0.0346 (18) | −0.073 (2) |
O4A | 0.087 (5) | 0.079 (4) | 0.0673 (18) | −0.003 (4) | −0.016 (3) | −0.0028 (19) |
O4B | 0.087 (5) | 0.079 (4) | 0.0673 (18) | −0.003 (4) | −0.016 (3) | −0.0028 (19) |
N1 | 0.0459 (13) | 0.0503 (15) | 0.0543 (14) | −0.0067 (11) | 0.0149 (11) | 0.0054 (12) |
N2 | 0.0492 (14) | 0.0526 (15) | 0.0531 (14) | −0.0009 (12) | 0.0190 (11) | 0.0060 (12) |
N3 | 0.0501 (13) | 0.0498 (15) | 0.0510 (13) | −0.0058 (11) | 0.0189 (11) | 0.0063 (11) |
N4 | 0.0455 (13) | 0.0468 (14) | 0.0571 (14) | −0.0038 (11) | 0.0216 (12) | 0.0010 (12) |
N5 | 0.0450 (13) | 0.0482 (14) | 0.0532 (14) | −0.0077 (11) | 0.0171 (11) | −0.0101 (11) |
N6 | 0.0508 (14) | 0.0569 (15) | 0.0488 (13) | −0.0154 (12) | 0.0213 (11) | −0.0098 (12) |
N7 | 0.0621 (15) | 0.0569 (16) | 0.0553 (15) | −0.0216 (12) | 0.0303 (12) | −0.0125 (12) |
N8 | 0.0509 (14) | 0.0565 (15) | 0.0502 (14) | −0.0094 (12) | 0.0245 (12) | −0.0103 (12) |
C1 | 0.0372 (14) | 0.0451 (16) | 0.0557 (17) | 0.0023 (12) | 0.0211 (13) | 0.0024 (13) |
C2 | 0.0500 (17) | 0.0523 (19) | 0.0585 (18) | −0.0045 (14) | 0.0216 (14) | 0.0037 (15) |
C3 | 0.0504 (17) | 0.0553 (19) | 0.0582 (18) | 0.0024 (14) | 0.0245 (15) | 0.0052 (15) |
C4 | 0.069 (2) | 0.072 (2) | 0.066 (2) | −0.0048 (18) | 0.0211 (18) | 0.0029 (19) |
C5 | 0.087 (3) | 0.100 (3) | 0.055 (2) | 0.000 (2) | 0.0179 (19) | 0.003 (2) |
C6 | 0.095 (3) | 0.098 (3) | 0.064 (2) | 0.013 (2) | 0.038 (2) | 0.028 (2) |
C7 | 0.087 (3) | 0.076 (3) | 0.076 (2) | −0.003 (2) | 0.042 (2) | 0.018 (2) |
C8 | 0.0583 (19) | 0.060 (2) | 0.064 (2) | 0.0051 (16) | 0.0310 (16) | 0.0096 (16) |
C9 | 0.088 (2) | 0.048 (2) | 0.086 (3) | −0.0155 (17) | 0.042 (2) | 0.0104 (18) |
C10 | 0.070 (2) | 0.0492 (19) | 0.082 (2) | −0.0197 (16) | 0.0325 (18) | −0.0020 (17) |
C11 | 0.0470 (16) | 0.0446 (17) | 0.0592 (19) | 0.0000 (13) | 0.0165 (14) | −0.0050 (14) |
C12 | 0.0521 (18) | 0.0489 (19) | 0.079 (2) | −0.0098 (15) | 0.0177 (16) | −0.0113 (17) |
C13 | 0.072 (2) | 0.063 (2) | 0.073 (2) | −0.0147 (18) | 0.0150 (19) | −0.0279 (19) |
C14 | 0.078 (2) | 0.078 (3) | 0.062 (2) | −0.008 (2) | 0.0219 (19) | −0.0232 (19) |
C15 | 0.063 (2) | 0.065 (2) | 0.059 (2) | −0.0064 (16) | 0.0241 (16) | −0.0103 (16) |
C16 | 0.0394 (14) | 0.0426 (16) | 0.0573 (17) | −0.0002 (12) | 0.0161 (13) | −0.0069 (13) |
C17 | 0.0421 (15) | 0.0474 (17) | 0.0526 (16) | −0.0009 (13) | 0.0197 (13) | −0.0052 (13) |
C18 | 0.0485 (16) | 0.0462 (17) | 0.0531 (17) | −0.0058 (13) | 0.0213 (13) | −0.0067 (14) |
C19 | 0.0501 (17) | 0.062 (2) | 0.0596 (19) | −0.0103 (15) | 0.0273 (15) | −0.0141 (16) |
C20 | 0.0495 (17) | 0.089 (3) | 0.0545 (19) | 0.0024 (17) | 0.0240 (15) | −0.0120 (18) |
C21 | 0.084 (2) | 0.153 (3) | 0.0590 (16) | 0.036 (2) | 0.0285 (15) | 0.0072 (19) |
C22 | 0.103 (3) | 0.139 (4) | 0.090 (3) | 0.032 (3) | 0.054 (3) | 0.025 (3) |
C23 | 0.084 (2) | 0.153 (3) | 0.0590 (16) | 0.036 (2) | 0.0285 (15) | 0.0072 (19) |
C24 | 0.0541 (15) | 0.160 (3) | 0.0641 (15) | 0.0115 (18) | 0.0051 (13) | −0.043 (2) |
C25 | 0.0541 (15) | 0.160 (3) | 0.0641 (15) | 0.0115 (18) | 0.0051 (13) | −0.043 (2) |
C26A | 0.074 (4) | 0.089 (5) | 0.070 (5) | −0.038 (4) | −0.004 (3) | −0.017 (4) |
C27A | 0.074 (4) | 0.089 (5) | 0.070 (5) | −0.038 (4) | −0.004 (3) | −0.017 (4) |
C26B | 0.092 (4) | 0.083 (4) | 0.076 (4) | −0.035 (3) | 0.014 (3) | −0.025 (3) |
C27B | 0.092 (4) | 0.083 (4) | 0.076 (4) | −0.035 (3) | 0.014 (3) | −0.025 (3) |
C28 | 0.066 (2) | 0.055 (2) | 0.078 (2) | −0.0124 (17) | 0.0193 (18) | −0.0151 (18) |
C29 | 0.072 (2) | 0.066 (3) | 0.121 (4) | −0.019 (2) | 0.029 (2) | −0.030 (3) |
C30 | 0.092 (3) | 0.063 (3) | 0.155 (4) | −0.028 (2) | 0.078 (3) | −0.028 (3) |
C31 | 0.110 (3) | 0.081 (3) | 0.103 (3) | −0.019 (2) | 0.070 (3) | 0.001 (2) |
C32 | 0.068 (2) | 0.069 (2) | 0.068 (2) | −0.0140 (17) | 0.0366 (17) | −0.0064 (18) |
C33 | 0.0470 (16) | 0.0460 (17) | 0.0605 (18) | −0.0023 (13) | 0.0260 (14) | −0.0089 (14) |
C34 | 0.0494 (16) | 0.0523 (18) | 0.0490 (16) | 0.0008 (14) | 0.0192 (14) | 0.0003 (14) |
N9 | 0.0627 (17) | 0.0598 (17) | 0.0654 (18) | −0.0071 (13) | 0.0227 (14) | −0.0041 (14) |
C35 | 0.085 (3) | 0.081 (3) | 0.089 (3) | −0.003 (2) | 0.043 (2) | −0.006 (2) |
C36 | 0.068 (3) | 0.090 (3) | 0.140 (4) | −0.021 (2) | 0.044 (3) | −0.004 (3) |
C37 | 0.076 (3) | 0.081 (3) | 0.094 (3) | −0.001 (2) | 0.003 (2) | −0.012 (3) |
C38 | 0.089 (3) | 0.059 (2) | 0.068 (2) | 0.014 (2) | 0.017 (2) | 0.0007 (18) |
C39 | 0.071 (2) | 0.054 (2) | 0.070 (2) | 0.0071 (17) | 0.0242 (18) | 0.0055 (17) |
N10 | 0.079 (2) | 0.080 (2) | 0.0663 (18) | 0.0029 (16) | 0.0360 (17) | −0.0070 (16) |
C40 | 0.075 (2) | 0.101 (3) | 0.064 (2) | 0.020 (2) | 0.031 (2) | 0.000 (2) |
C41 | 0.099 (3) | 0.095 (3) | 0.055 (2) | 0.017 (2) | 0.021 (2) | 0.002 (2) |
C42 | 0.120 (4) | 0.093 (3) | 0.073 (3) | 0.038 (3) | 0.061 (3) | 0.022 (2) |
C43 | 0.102 (3) | 0.081 (3) | 0.114 (3) | 0.022 (2) | 0.075 (3) | 0.034 (3) |
C44 | 0.089 (3) | 0.071 (3) | 0.086 (3) | −0.004 (2) | 0.045 (2) | 0.006 (2) |
N11 | 0.0665 (17) | 0.072 (2) | 0.0841 (19) | −0.0186 (15) | 0.0462 (16) | −0.0158 (16) |
C45 | 0.095 (3) | 0.080 (3) | 0.110 (3) | −0.017 (2) | 0.070 (3) | −0.030 (2) |
C46 | 0.092 (3) | 0.076 (3) | 0.106 (3) | −0.032 (2) | 0.050 (3) | −0.022 (2) |
C47 | 0.054 (2) | 0.102 (3) | 0.095 (3) | −0.013 (2) | 0.035 (2) | 0.008 (2) |
C48 | 0.059 (2) | 0.086 (3) | 0.078 (2) | 0.0127 (19) | 0.0357 (18) | 0.006 (2) |
C49 | 0.073 (2) | 0.063 (2) | 0.063 (2) | −0.0028 (17) | 0.0347 (18) | −0.0010 (16) |
S1—C1 | 1.666 (3) | C21—H21A | 0.9300 |
S2—C18 | 1.657 (3) | C22—C23 | 1.370 (6) |
O1—C8 | 1.375 (4) | C22—H22A | 0.9300 |
O1—C9 | 1.420 (4) | C23—C24 | 1.346 (6) |
O2—C11 | 1.371 (3) | C23—H23A | 0.9300 |
O2—C10 | 1.430 (3) | C24—C25 | 1.406 (5) |
O3—C25 | 1.370 (4) | C24—H24A | 0.9300 |
O3—C26A | 1.437 (5) | C26A—C27A | 1.453 (5) |
O3—C26B | 1.467 (4) | C26A—H26A | 0.9700 |
O4A—C28 | 1.371 (5) | C26A—H26B | 0.9700 |
O4A—C27A | 1.438 (5) | C27A—H27A | 0.9700 |
O4B—C28 | 1.390 (5) | C27A—H27B | 0.9700 |
O4B—C27B | 1.448 (4) | C26B—C27B | 1.466 (5) |
N1—C1 | 1.352 (3) | C26B—H26C | 0.9700 |
N1—N2 | 1.379 (3) | C26B—H26D | 0.9700 |
N1—H1A | 0.8600 | C27B—H27C | 0.9700 |
N2—C2 | 1.276 (4) | C27B—H27D | 0.9700 |
N3—C1 | 1.353 (3) | C28—C29 | 1.380 (5) |
N3—N4 | 1.377 (3) | C28—C33 | 1.401 (4) |
N3—H3A | 0.8600 | C29—C30 | 1.359 (6) |
N4—C34 | 1.276 (3) | C29—H29A | 0.9300 |
N5—C17 | 1.273 (3) | C30—C31 | 1.377 (6) |
N5—N6 | 1.381 (3) | C30—H30A | 0.9300 |
N6—C18 | 1.350 (3) | C31—C32 | 1.381 (5) |
N6—H6A | 0.8600 | C31—H31A | 0.9300 |
N7—C18 | 1.362 (3) | C32—C33 | 1.376 (4) |
N7—N8 | 1.374 (3) | C32—H32A | 0.9300 |
N7—H7A | 0.8600 | C33—C34 | 1.461 (4) |
N8—C19 | 1.280 (3) | C34—H34A | 0.9300 |
C2—C3 | 1.457 (4) | N9—C35 | 1.324 (4) |
C2—H2B | 0.9300 | N9—C39 | 1.327 (4) |
C3—C4 | 1.396 (4) | C35—C36 | 1.395 (5) |
C3—C8 | 1.399 (4) | C35—H35A | 0.9300 |
C4—C5 | 1.378 (5) | C36—C37 | 1.370 (6) |
C4—H4B | 0.9300 | C36—H36A | 0.9300 |
C5—C6 | 1.376 (5) | C37—C38 | 1.349 (6) |
C5—H5B | 0.9300 | C37—H37A | 0.9300 |
C6—C7 | 1.375 (5) | C38—C39 | 1.360 (5) |
C6—H6B | 0.9300 | C38—H38A | 0.9300 |
C7—C8 | 1.378 (4) | C39—H39A | 0.9300 |
C7—H7B | 0.9300 | N10—C40 | 1.305 (4) |
C9—C10 | 1.486 (5) | N10—C44 | 1.330 (4) |
C9—H9A | 0.9700 | C40—C41 | 1.390 (5) |
C9—H9B | 0.9700 | C40—H40A | 0.9300 |
C10—H10A | 0.9700 | C41—C42 | 1.338 (5) |
C10—H10B | 0.9700 | C41—H41A | 0.9300 |
C11—C16 | 1.393 (4) | C42—C43 | 1.387 (6) |
C11—C12 | 1.396 (4) | C42—H42A | 0.9300 |
C12—C13 | 1.368 (5) | C43—C44 | 1.382 (5) |
C12—H12A | 0.9300 | C43—H43A | 0.9300 |
C13—C14 | 1.370 (5) | C44—H44A | 0.9300 |
C13—H13A | 0.9300 | N11—C49 | 1.318 (4) |
C14—C15 | 1.390 (4) | N11—C45 | 1.326 (4) |
C14—H14A | 0.9300 | C45—C46 | 1.379 (5) |
C15—C16 | 1.393 (4) | C45—H45A | 0.9300 |
C15—H15A | 0.9300 | C46—C47 | 1.356 (5) |
C16—C17 | 1.468 (4) | C46—H46A | 0.9300 |
C17—H17A | 0.9300 | C47—C48 | 1.354 (5) |
C19—C20 | 1.444 (4) | C47—H47A | 0.9300 |
C19—H19A | 0.9300 | C48—C49 | 1.362 (4) |
C20—C21 | 1.379 (6) | C48—H48A | 0.9300 |
C20—C25 | 1.409 (5) | C49—H49A | 0.9300 |
C21—C22 | 1.401 (5) | ||
C8—O1—C9 | 118.1 (3) | C25—C24—H24A | 119.6 |
C11—O2—C10 | 118.5 (2) | O3—C25—C24 | 124.9 (4) |
C25—O3—C26A | 99.5 (5) | O3—C25—C20 | 115.8 (3) |
C25—O3—C26B | 129.7 (5) | C24—C25—C20 | 119.2 (4) |
C26A—O3—C26B | 30.9 (4) | O3—C26A—C27A | 95.0 (7) |
C28—O4A—C27A | 116.1 (7) | O3—C26A—H26A | 112.7 |
C28—O4B—C27B | 122.0 (6) | C27A—C26A—H26A | 112.7 |
C1—N1—N2 | 122.2 (2) | O3—C26A—H26B | 112.7 |
C1—N1—H1A | 118.9 | C27A—C26A—H26B | 112.7 |
N2—N1—H1A | 118.9 | H26A—C26A—H26B | 110.2 |
C2—N2—N1 | 114.0 (2) | O4A—C27A—C26A | 100.2 (6) |
C1—N3—N4 | 119.5 (2) | O4A—C27A—H27A | 111.7 |
C1—N3—H3A | 120.3 | C26A—C27A—H27A | 111.7 |
N4—N3—H3A | 120.3 | O4A—C27A—H27B | 111.7 |
C34—N4—N3 | 115.6 (2) | C26A—C27A—H27B | 111.7 |
C17—N5—N6 | 116.1 (2) | H27A—C27A—H27B | 109.5 |
C18—N6—N5 | 120.2 (2) | C27B—C26B—O3 | 115.4 (6) |
C18—N6—H6A | 119.9 | C27B—C26B—H26C | 108.4 |
N5—N6—H6A | 119.9 | O3—C26B—H26C | 108.4 |
C18—N7—N8 | 121.1 (2) | C27B—C26B—H26D | 108.4 |
C18—N7—H7A | 119.4 | O3—C26B—H26D | 108.4 |
N8—N7—H7A | 119.4 | H26C—C26B—H26D | 107.5 |
C19—N8—N7 | 114.8 (2) | O4B—C27B—C26B | 113.3 (7) |
N1—C1—N3 | 114.6 (2) | O4B—C27B—H27C | 108.9 |
N1—C1—S1 | 119.5 (2) | C26B—C27B—H27C | 108.9 |
N3—C1—S1 | 125.9 (2) | O4B—C27B—H27D | 108.9 |
N2—C2—C3 | 123.6 (3) | C26B—C27B—H27D | 108.9 |
N2—C2—H2B | 118.2 | H27C—C27B—H27D | 107.7 |
C3—C2—H2B | 118.2 | O4A—C28—C29 | 118.5 (6) |
C4—C3—C8 | 118.3 (3) | O4A—C28—O4B | 25.8 (7) |
C4—C3—C2 | 123.4 (3) | C29—C28—O4B | 126.5 (5) |
C8—C3—C2 | 118.3 (3) | O4A—C28—C33 | 120.0 (6) |
C5—C4—C3 | 120.5 (4) | C29—C28—C33 | 119.9 (3) |
C5—C4—H4B | 119.8 | O4B—C28—C33 | 112.2 (4) |
C3—C4—H4B | 119.8 | C30—C29—C28 | 120.5 (4) |
C6—C5—C4 | 120.2 (4) | C30—C29—H29A | 119.7 |
C6—C5—H5B | 119.9 | C28—C29—H29A | 119.7 |
C4—C5—H5B | 119.9 | C29—C30—C31 | 120.5 (4) |
C7—C6—C5 | 120.5 (3) | C29—C30—H30A | 119.7 |
C7—C6—H6B | 119.8 | C31—C30—H30A | 119.7 |
C5—C6—H6B | 119.8 | C30—C31—C32 | 119.5 (4) |
C6—C7—C8 | 119.8 (4) | C30—C31—H31A | 120.2 |
C6—C7—H7B | 120.1 | C32—C31—H31A | 120.2 |
C8—C7—H7B | 120.1 | C33—C32—C31 | 121.0 (3) |
O1—C8—C7 | 123.2 (3) | C33—C32—H32A | 119.5 |
O1—C8—C3 | 115.9 (3) | C31—C32—H32A | 119.5 |
C7—C8—C3 | 120.8 (3) | C32—C33—C28 | 118.6 (3) |
O1—C9—C10 | 108.4 (3) | C32—C33—C34 | 122.0 (3) |
O1—C9—H9A | 110.0 | C28—C33—C34 | 119.3 (3) |
C10—C9—H9A | 110.0 | N4—C34—C33 | 120.9 (3) |
O1—C9—H9B | 110.0 | N4—C34—H34A | 119.5 |
C10—C9—H9B | 110.0 | C33—C34—H34A | 119.5 |
H9A—C9—H9B | 108.4 | C35—N9—C39 | 116.3 (3) |
O2—C10—C9 | 107.4 (3) | N9—C35—C36 | 122.8 (4) |
O2—C10—H10A | 110.2 | N9—C35—H35A | 118.6 |
C9—C10—H10A | 110.2 | C36—C35—H35A | 118.6 |
O2—C10—H10B | 110.2 | C37—C36—C35 | 117.9 (4) |
C9—C10—H10B | 110.2 | C37—C36—H36A | 121.0 |
H10A—C10—H10B | 108.5 | C35—C36—H36A | 121.0 |
O2—C11—C16 | 116.3 (2) | C38—C37—C36 | 119.9 (4) |
O2—C11—C12 | 123.8 (3) | C38—C37—H37A | 120.1 |
C16—C11—C12 | 119.9 (3) | C36—C37—H37A | 120.1 |
C13—C12—C11 | 119.9 (3) | C37—C38—C39 | 117.9 (4) |
C13—C12—H12A | 120.1 | C37—C38—H38A | 121.0 |
C11—C12—H12A | 120.1 | C39—C38—H38A | 121.0 |
C12—C13—C14 | 121.5 (3) | N9—C39—C38 | 125.1 (4) |
C12—C13—H13A | 119.3 | N9—C39—H39A | 117.5 |
C14—C13—H13A | 119.3 | C38—C39—H39A | 117.5 |
C13—C14—C15 | 119.0 (3) | C40—N10—C44 | 116.8 (3) |
C13—C14—H14A | 120.5 | N10—C40—C41 | 124.1 (4) |
C15—C14—H14A | 120.5 | N10—C40—H40A | 117.9 |
C14—C15—C16 | 121.0 (3) | C41—C40—H40A | 117.9 |
C14—C15—H15A | 119.5 | C42—C41—C40 | 119.3 (4) |
C16—C15—H15A | 119.5 | C42—C41—H41A | 120.3 |
C11—C16—C15 | 118.7 (3) | C40—C41—H41A | 120.3 |
C11—C16—C17 | 120.5 (3) | C41—C42—C43 | 117.8 (4) |
C15—C16—C17 | 120.7 (3) | C41—C42—H42A | 121.1 |
N5—C17—C16 | 119.8 (3) | C43—C42—H42A | 121.1 |
N5—C17—H17A | 120.1 | C44—C43—C42 | 119.1 (4) |
C16—C17—H17A | 120.1 | C44—C43—H43A | 120.5 |
N6—C18—N7 | 113.2 (2) | C42—C43—H43A | 120.5 |
N6—C18—S2 | 126.3 (2) | N10—C44—C43 | 122.8 (4) |
N7—C18—S2 | 120.5 (2) | N10—C44—H44A | 118.6 |
N8—C19—C20 | 122.5 (3) | C43—C44—H44A | 118.6 |
N8—C19—H19A | 118.8 | C49—N11—C45 | 116.6 (3) |
C20—C19—H19A | 118.8 | N11—C45—C46 | 123.2 (3) |
C21—C20—C25 | 118.0 (3) | N11—C45—H45A | 118.4 |
C21—C20—C19 | 122.2 (3) | C46—C45—H45A | 118.4 |
C25—C20—C19 | 119.8 (3) | C47—C46—C45 | 118.4 (4) |
C20—C21—C22 | 122.0 (5) | C47—C46—H46A | 120.8 |
C20—C21—H21A | 119.0 | C45—C46—H46A | 120.8 |
C22—C21—H21A | 119.0 | C48—C47—C46 | 119.1 (3) |
C23—C22—C21 | 118.4 (5) | C48—C47—H47A | 120.5 |
C23—C22—H22A | 120.8 | C46—C47—H47A | 120.5 |
C21—C22—H22A | 120.8 | C47—C48—C49 | 118.9 (3) |
C24—C23—C22 | 121.5 (4) | C47—C48—H48A | 120.6 |
C24—C23—H23A | 119.2 | C49—C48—H48A | 120.6 |
C22—C23—H23A | 119.2 | N11—C49—C48 | 123.8 (3) |
C23—C24—C25 | 120.9 (4) | N11—C49—H49A | 118.1 |
C23—C24—H24A | 119.6 | C48—C49—H49A | 118.1 |
C1—N1—N2—C2 | 179.9 (3) | C26A—O3—C25—C20 | 154.9 (5) |
C1—N3—N4—C34 | −176.8 (2) | C26B—O3—C25—C20 | 147.4 (5) |
C17—N5—N6—C18 | −177.4 (3) | C23—C24—C25—O3 | −179.5 (4) |
C18—N7—N8—C19 | 175.9 (3) | C23—C24—C25—C20 | −2.0 (6) |
N2—N1—C1—N3 | 0.1 (4) | C21—C20—C25—O3 | 179.8 (3) |
N2—N1—C1—S1 | −179.3 (2) | C19—C20—C25—O3 | −1.1 (5) |
N4—N3—C1—N1 | 175.5 (2) | C21—C20—C25—C24 | 2.1 (5) |
N4—N3—C1—S1 | −5.2 (4) | C19—C20—C25—C24 | −178.8 (3) |
N1—N2—C2—C3 | −179.4 (3) | C25—O3—C26A—C27A | −145.9 (6) |
N2—C2—C3—C4 | 7.3 (5) | C26B—O3—C26A—C27A | 22.8 (8) |
N2—C2—C3—C8 | −172.1 (3) | C28—O4A—C27A—C26A | −165.0 (10) |
C8—C3—C4—C5 | −0.2 (5) | O3—C26A—C27A—O4A | 67.3 (11) |
C2—C3—C4—C5 | −179.7 (3) | C25—O3—C26B—C27B | −53.6 (10) |
C3—C4—C5—C6 | 0.9 (6) | C26A—O3—C26B—C27B | −68.0 (10) |
C4—C5—C6—C7 | −1.1 (6) | C28—O4B—C27B—C26B | −59.4 (13) |
C5—C6—C7—C8 | 0.6 (6) | O3—C26B—C27B—O4B | −53.3 (12) |
C9—O1—C8—C7 | −42.7 (4) | C27A—O4A—C28—C29 | −17.0 (15) |
C9—O1—C8—C3 | 139.6 (3) | C27A—O4A—C28—O4B | −133 (3) |
C6—C7—C8—O1 | −177.5 (3) | C27A—O4A—C28—C33 | 148.4 (10) |
C6—C7—C8—C3 | 0.1 (5) | C27B—O4B—C28—O4A | 43.9 (15) |
C4—C3—C8—O1 | 177.5 (3) | C27B—O4B—C28—C29 | −36.4 (12) |
C2—C3—C8—O1 | −3.1 (4) | C27B—O4B—C28—C33 | 157.2 (7) |
C4—C3—C8—C7 | −0.3 (5) | O4A—C28—C29—C30 | 165.8 (8) |
C2—C3—C8—C7 | 179.2 (3) | O4B—C28—C29—C30 | −165.0 (6) |
C8—O1—C9—C10 | −150.0 (3) | C33—C28—C29—C30 | 0.4 (6) |
C11—O2—C10—C9 | −179.0 (3) | C28—C29—C30—C31 | 0.1 (6) |
O1—C9—C10—O2 | 64.8 (4) | C29—C30—C31—C32 | 0.0 (6) |
C10—O2—C11—C16 | 170.8 (3) | C30—C31—C32—C33 | −0.7 (6) |
C10—O2—C11—C12 | −8.7 (4) | C31—C32—C33—C28 | 1.2 (5) |
O2—C11—C12—C13 | −178.8 (3) | C31—C32—C33—C34 | −176.8 (3) |
C16—C11—C12—C13 | 1.7 (5) | O4A—C28—C33—C32 | −166.2 (7) |
C11—C12—C13—C14 | 1.0 (5) | C29—C28—C33—C32 | −1.1 (5) |
C12—C13—C14—C15 | −2.2 (6) | O4B—C28—C33—C32 | 166.3 (5) |
C13—C14—C15—C16 | 0.7 (5) | O4A—C28—C33—C34 | 11.8 (8) |
O2—C11—C16—C15 | 177.3 (3) | C29—C28—C33—C34 | 177.0 (3) |
C12—C11—C16—C15 | −3.2 (4) | O4B—C28—C33—C34 | −15.6 (6) |
O2—C11—C16—C17 | −5.8 (4) | N3—N4—C34—C33 | 178.0 (2) |
C12—C11—C16—C17 | 173.7 (3) | C32—C33—C34—N4 | −1.5 (4) |
C14—C15—C16—C11 | 2.0 (5) | C28—C33—C34—N4 | −179.6 (3) |
C14—C15—C16—C17 | −174.9 (3) | C39—N9—C35—C36 | −0.2 (5) |
N6—N5—C17—C16 | 178.6 (2) | N9—C35—C36—C37 | 1.1 (6) |
C11—C16—C17—N5 | 178.1 (3) | C35—C36—C37—C38 | −1.2 (7) |
C15—C16—C17—N5 | −5.1 (4) | C36—C37—C38—C39 | 0.3 (6) |
N5—N6—C18—N7 | 179.4 (2) | C35—N9—C39—C38 | −0.8 (5) |
N5—N6—C18—S2 | −1.4 (4) | C37—C38—C39—N9 | 0.7 (5) |
N8—N7—C18—N6 | 8.6 (4) | C44—N10—C40—C41 | −0.8 (6) |
N8—N7—C18—S2 | −170.6 (2) | N10—C40—C41—C42 | 0.1 (6) |
N7—N8—C19—C20 | −177.3 (3) | C40—C41—C42—C43 | 0.2 (6) |
N8—C19—C20—C21 | 3.1 (5) | C41—C42—C43—C44 | 0.1 (6) |
N8—C19—C20—C25 | −175.9 (3) | C40—N10—C44—C43 | 1.1 (5) |
C25—C20—C21—C22 | −1.7 (6) | C42—C43—C44—N10 | −0.8 (6) |
C19—C20—C21—C22 | 179.2 (3) | C49—N11—C45—C46 | −0.8 (6) |
C20—C21—C22—C23 | 1.1 (6) | N11—C45—C46—C47 | 0.2 (7) |
C21—C22—C23—C24 | −0.9 (7) | C45—C46—C47—C48 | 0.7 (6) |
C22—C23—C24—C25 | 1.4 (7) | C46—C47—C48—C49 | −1.0 (6) |
C26A—O3—C25—C24 | −27.6 (6) | C45—N11—C49—C48 | 0.5 (5) |
C26B—O3—C25—C24 | −35.0 (7) | C47—C48—C49—N11 | 0.4 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N9i | 0.86 | 2.14 | 2.990 (4) | 173 |
N3—H3A···N10 | 0.86 | 2.32 | 3.061 (4) | 144 |
N7—H7A···N11 | 0.86 | 2.17 | 3.008 (4) | 164 |
C40—H40A···Cg1 | 0.93 | 2.76 | 3.453 (5) | 132 |
C45—H45A···Cg2 | 0.93 | 2.87 | 3.673 (5) | 146 |
C13—H13A···Cg3ii | 0.93 | 2.75 | 3.522 (4) | 141 |
C36—H36A···Cg2iii | 0.93 | 2.94 | 3.746 (5) | 146 |
C46—H46A···Cg4iv | 0.93 | 2.94 | 3.769 (5) | 149 |
Symmetry codes: (i) x−1, y, z; (ii) −x, y−1/2, −z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C34H32N8O4S2·3C5H5N |
Mr | 918.10 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 12.1752 (2), 22.2029 (1), 19.8479 (4) |
β (°) | 117.168 (1) |
V (Å3) | 4773.42 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.17 |
Crystal size (mm) | 0.37 × 0.33 × 0.28 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.941, 0.955 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 30445, 10907, 5918 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.166, 1.05 |
No. of reflections | 10907 |
No. of parameters | 593 |
No. of restraints | 9 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.46, −0.49 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL and PLATON (Spek, 1990).
S1—C1 | 1.666 (3) | S2—C18 | 1.657 (3) |
N1—C1—N3 | 114.6 (2) | N6—C18—N7 | 113.2 (2) |
N1—C1—S1 | 119.5 (2) | N6—C18—S2 | 126.3 (2) |
N3—C1—S1 | 125.9 (2) | N7—C18—S2 | 120.5 (2) |
O1—C9—C10—O2 | 64.8 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N9i | 0.86 | 2.1346 | 2.990 (4) | 173 |
N3—H3A···N10 | 0.86 | 2.3209 | 3.061 (4) | 144 |
N7—H7A···N11 | 0.86 | 2.1733 | 3.008 (4) | 164 |
C40—H40A···Cg1 | 0.93 | 2.757 | 3.453 (5) | 132 |
C45—H45A···Cg2 | 0.93 | 2.868 | 3.673 (5) | 146 |
C13—H13A···Cg3ii | 0.93 | 2.752 | 3.522 (4) | 141 |
C36—H36A···Cg2iii | 0.93 | 2.942 | 3.746 (5) | 146 |
C46—H46A···Cg4iv | 0.93 | 2.941 | 3.769 (5) | 149 |
Symmetry codes: (i) x−1, y, z; (ii) −x, y−1/2, −z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+1, y+1/2, −z+1/2. |
Thiocarbohydrazide, H2NHNC(S)NHNH2, and its Schiff base derivatives are interesting ligand systems because of the availability of several different kinds of potential donor sites (Bustos et al., 1990; Bacchi et al., 1996; Souza et al., 1994). Recently, many open-chain ligands of thiocarbohydrazone have been rapidly developed and studied in detail. The aim of the present research is the design of a new macrocyclic ligand involving mixed N, S and O donor atoms, and we describe here the synthesis and characterization of a novel 30-member 2:2 macrocyclic thiocarbohydrazone, (I), obtained by the condensation of thiocarbohydrazide with 1,4-bis(2'-formylphenyl)-1,4-dioxabutane. \sch
As shown in Fig. 1, the molecule of (I) is twisted. The S1—C1 [1.666 (3) Å] and S2—C18 [1.657 (3) Å] distances indicate that they are double bonds (Bustos et al., 1990; Bacchi et al., 1996). This suggests the presence of thioketo form in the solid state. The torsion angle along the O1—C9—C10—O2 bond of the dioxabutane is 64.8 (4)°. This dioxabutane group is boat-like in shape, whereas the other is highly disordered (atoms O4, C26 and C27 are disordered).
Each unit of the macrocyclic ring, consisting of the thiocarbohydrazone and the axially substituted phenyl rings, adopts a planar conformation. The dihedral angles are 15.4 (2)° between rings C3—C8 and C28—C33, and 12.6 (2)° between rings C11—C16 and C20—C25. The twist is introduced by the dioxabutane bridges connecting the two units. The dihedral angle between the two thiocarbohydrazone groups is 30.98 (8)°.
The three molecules of pyridine present as solvate in (I) help to stabilize the structure by forming intra- and intermolecular hydrogen bonds with the macrocyclic ring; details are given in Table 2. The C—H···Cg(π-ring) interactions [Cg1 = C20—C25, Cg2 = C28—C33, Cg3 = N10 and C40—C44 (one of the three pyridine molecules), and Cg4 = C11—C16], i.e. the interaction between the H atoms of the phenyl rings and the centre of gravity of the pyridine rings and vice versa, play a major role in the packing and molecular arrangement in the crystal (Table 2).