organic compounds
meso-(1S*,21R*)-25-Methyl-8,11,14-trioxa-22,24,25-triazatetracyclo[19.3.1.02,7.015,20]pentacosa-2,4,6,15(20),16,18-hexaene-23-thione chloroform monosolvate
aDepartment of Chemistry, Vietnam National University, 144 Xuan Thuy, Cau Giay, Hanoi, Vietnam, bOrganic Chemistry Department, Russian Peoples Friendship University, Miklukho-Maklaya St. 6, Moscow, 117198, Russia, and cX-Ray Structural Centre, A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov St., B-334, Moscow 119991, Russian Federation
*Correspondence e-mail: thh1101@yahoo.com
The title compound crystallizes as a chloroform solvate, C20H23N3O3S·CHCl3, with two crystallographically independent units. The independent units have distinctly different interaction patterns between the azacrown macrocycle and the chloroform solvent molecule. In one of them, the chloroform molecule forms C—H⋯N and Cl⋯H—C hydrogen bonds with the azacrown macrocycle (as a proton donor and an acceptor, respectively), whereas in the other, one of the chloroform molecules is bound to the azacrown macrocycle by an attractive Cl⋯O [3.080 (3) Å] interaction. The azacrown macrocycles of different units are structurally similar; the aza-14-crown-3-ether ring adopts a bowl conformation with dihedral angles between the planes of the fused benzene rings of 60.7 (1) and 68.0 (1)°. The triazinanethione ring in both cases has a sofa conformation. The crystal packing is characterized by N—H⋯S, N—H⋯O, C—H⋯Cl and C—H⋯S hydrogen bonds.
Related literature
For general background, see: Hiraoka (1982); Pedersen (1988); Gokel & Murillo (1996); Bradshaw & Izatt (1997). For related compounds, see: Levov et al. (2006, 2008); Anh et al. (2008, 2012a,b); Hieu et al. (2009, 2011); Khieu et al. (2011).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2005); cell SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536812037051/ld2071sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812037051/ld2071Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812037051/ld2071Isup3.cml
Methylamine ammonium acetate (4.0 g, 44 mmol) was added to a solution of 1,5-bis(2-formylphenoxy)-3-oxapentane (1.57 g, 5.0 mmol) and thiourea (0.38 g, 5.0 mmol) in a mixture of ethanol (30 ml) and acetic acid (1 ml). The reaction mixture was stirred at 293 K for 3 days. At the end of the reaction, the formed precipitate was filtered off, washed with ethanol and re-crystallized from ethanol and ethylacetate (4:1) to give 1.19 g of white crystals of I. Yield is 61.8%. M.p. = 417–419 K. IR (KBr), ν/cm-1: 1603, 3215, 3332. 1HNMR (DMSO-d6, 400 MHz, 300 K): δ = 1.53 (s, 3H, CH3), 3.63 and 3.92 (both m, 3H and 5H, respectively, OCH2CH2OCH2CH2O), 6.21 (s, 2H, H1 and H21), 6.87 (d, 2H, J = 8.0, H6 and H16), 6.91 (tt, 2H, J = 7.6 and 0.8, H4 and H18), 7.25–7.30 (m, 4H, Harom), 8.27 (s, 2H, NH). Anal. Calcd for C20H23N3O3S: C, 62.32; H, 6.01; N, 10.90. Found: C, 62.51; H, 6.15; N, 10.86.
There are two relatively high positive peaks of 1.38 and 1.24 e Å-3 near the Cl5 and Cl4 chlorine atoms of the solvate chloroform molecule that indicate a slight disorder of the solvate molecule. However, due to the low contribution of the second component it was neglected.
The hydrogen atoms of the amino groups were localized in the difference-Fourier map and included in the
with fixed positional and isotropic displacement parameters [Uĩso~(H) = 1.2U~eq~(N)]. Other hydrogen atoms were placed in calculated positions with C—H = 0.95–1.00 Å and refined in the riding model with fixed isotropic displacement parameters [Uĩso~(H) = 1.5U~eq~(C) for the methyl group and 1.2U~eq~(C) for the other groups].Supramolecular chemistry of azacrown
draws a great attention of researchers during the last decades (Hiraoka, 1982; Pedersen, 1988; Gokel & Murillo, 1996; Bradshaw & Izatt, 1997). Recently, we have developed effective methods of synthesis of azacrown containing piperidine (Levov et al., 2006, 2008; Anh et al., 2008, 2012a, 2012b), perhydropyrimidine (Hieu et al., 2011) and perhydrotriazine (Hieu et al., 2009; Khieu et al., 2011) subunits.In an attempt to apply these for a synthesis of a macrocyclic ligand with an N-methylsubstituted perhydrotriazine moiety, we studied the multicomponent condensation of thiourea with 1,5-bis(2-formylphenoxy)-3-oxapentane and methylammonium acetate. The reaction has proceeded smoothly under mild conditions to give the expected azacrown moiety in a good yield (Figure 1).
Compound I crystallizes as a chloroform solvate, i. e., C20H23N3O3S.CHCl3, with two crystallographically independent units within the
These crystallographically independent units represent two different molecular I.CHCl3 associates distinguished by different interactions between I and CHCl3 counterparts. In one of the two associates, the chloroform molecule forms the two C53—H53···N25 (as a protonodonor) and Cl2···H26A—C26 (as a protonoacceptor) hydrogen bonds (Table 1, Figure 2a), whereas, in the other associate, the chloroform molecule is bound to the molecule I by the attractive Cl6···O37 (3.080 (3) Å) interaction (Figure 2b). The azacrown macrocycles of the different I.CHCl3 associates are structurally similar.The aza-14-crown-3-ether ring adopts a bowl conformation. The configuration of the C7—O8—C9—C10 —O11—C12—C13—O14—C15 polyether chain is t–g(-)–t–t–g(+)–t (t = trans, 180°; g = gauche, ±60°). The dihedral angles between the planes of the benzene rings fused to the aza-14-crown-3-ether moiety are 60.69 (8) and 68.01 (5)° for two crystallographically independent molecules, respectively. The triazinanethione ring has a sofa conformation - the nitrogen atoms N22, N24, N48 and N50 have a trigonal-planar geometry (sums of the bond angles are 358.8, 360.0, 359.0 and 359.9°, respectively), while the nitrogen N25 and N51 atoms adopt a trigonal-pyramidal geometry (sums of the bond angles are 331.9 and 333.7°, respectively).
The molecule of I possesses two asymmetric centers at the C1 and C21 carbon atoms and represents a meso-form (an internal racemate).
In the crystal, the molecular I.CHCl3 associates are linked by the intermolecular N—H···S, N—H···O, C—H···Cl and C—H···S hydrogen bonds into a three-dimensional framework (Table 1).
For general background, see: Hiraoka (1982); Pedersen (1988); Gokel & Murillo (1996); Bradshaw & Izatt (1997). For related compounds, see: Levov et al. (2006, 2008); Anh et al. (2008, 2012a,b); Hieu et al. (2009, 2011); Khieu et al. (2011).
Data collection: APEX2 (Bruker, 2005); cell
SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. Multicomponent condensation of thiourea with 1,5-bis(2-formylphenoxy)-3-oxapentane and methylammonium acetate. | |
Fig. 2. Molecular structure of I (first crystallographically independent I.CHCl3 unit is depicted). Displacement ellipsoids are shown at 50% probability level. Dashed lines indicate intermolecular hydrogen bonds and attractive O···Cl interaction. H atoms are presented as small spheres of arbitrary radius. | |
Fig. 3. Molecular structure of I (second crystallographically independent I.CHCl3 unit is depicted). Displacement ellipsoids are shown at 50% probability level. Dashed lines indicate intermolecular hydrogen bonds and attractive O···Cl interaction. H atoms are presented as small spheres of arbitrary radius. |
C20H23N3O3S·CHCl3 | F(000) = 2096 |
Mr = 504.84 | Dx = 1.436 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 8820 reflections |
a = 17.8370 (5) Å | θ = 2.3–31.3° |
b = 13.9173 (4) Å | µ = 0.51 mm−1 |
c = 19.0561 (6) Å | T = 100 K |
β = 99.222 (1)° | Prism, colourless |
V = 4669.4 (2) Å3 | 0.30 × 0.25 × 0.20 mm |
Z = 8 |
Bruker APEXII CCD diffractometer | 11281 independent reflections |
Radiation source: fine-focus sealed tube | 8711 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
φ and ω scans | θmax = 28.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −23→23 |
Tmin = 0.862, Tmax = 0.905 | k = −18→18 |
52534 measured reflections | l = −25→25 |
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)] = 0.051 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.145 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0795P)2 + 4P] where P = (Fo2 + 2Fc2)/3 |
11281 reflections | (Δ/σ)max = 0.001 |
561 parameters | Δρmax = 1.38 e Å−3 |
0 restraints | Δρmin = −1.05 e Å−3 |
C20H23N3O3S·CHCl3 | V = 4669.4 (2) Å3 |
Mr = 504.84 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 17.8370 (5) Å | µ = 0.51 mm−1 |
b = 13.9173 (4) Å | T = 100 K |
c = 19.0561 (6) Å | 0.30 × 0.25 × 0.20 mm |
β = 99.222 (1)° |
Bruker APEXII CCD diffractometer | 11281 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 8711 reflections with I > 2σ(I) |
Tmin = 0.862, Tmax = 0.905 | Rint = 0.052 |
52534 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.145 | H-atom parameters constrained |
S = 1.00 | Δρmax = 1.38 e Å−3 |
11281 reflections | Δρmin = −1.05 e Å−3 |
561 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.40501 (3) | 1.09117 (4) | 0.46981 (3) | 0.01438 (12) | |
C1 | 0.39732 (11) | 0.83090 (15) | 0.37434 (11) | 0.0123 (4) | |
H1 | 0.4035 | 0.8478 | 0.3246 | 0.015* | |
C2 | 0.44422 (12) | 0.74267 (15) | 0.39512 (12) | 0.0140 (4) | |
C3 | 0.48141 (12) | 0.72432 (16) | 0.46368 (12) | 0.0168 (4) | |
H3 | 0.4787 | 0.7700 | 0.5002 | 0.020* | |
C4 | 0.52264 (14) | 0.63971 (18) | 0.47951 (14) | 0.0228 (5) | |
H4 | 0.5486 | 0.6284 | 0.5263 | 0.027* | |
C5 | 0.52547 (14) | 0.57230 (17) | 0.42640 (14) | 0.0240 (5) | |
H5 | 0.5533 | 0.5145 | 0.4372 | 0.029* | |
C6 | 0.48805 (13) | 0.58815 (17) | 0.35750 (14) | 0.0211 (5) | |
H6 | 0.4903 | 0.5416 | 0.3214 | 0.025* | |
C7 | 0.44703 (12) | 0.67319 (16) | 0.34181 (12) | 0.0161 (4) | |
O8 | 0.40804 (9) | 0.69639 (12) | 0.27653 (8) | 0.0191 (3) | |
C9 | 0.40705 (13) | 0.62893 (17) | 0.21950 (12) | 0.0185 (5) | |
H9A | 0.3817 | 0.5687 | 0.2304 | 0.022* | |
H9B | 0.4596 | 0.6135 | 0.2126 | 0.022* | |
C10 | 0.36434 (13) | 0.67444 (18) | 0.15376 (12) | 0.0196 (5) | |
H10A | 0.3837 | 0.7402 | 0.1484 | 0.024* | |
H10B | 0.3719 | 0.6366 | 0.1115 | 0.024* | |
O11 | 0.28513 (9) | 0.67811 (12) | 0.15886 (8) | 0.0179 (3) | |
C12 | 0.24553 (14) | 0.75651 (17) | 0.12146 (12) | 0.0202 (5) | |
H12A | 0.2291 | 0.7388 | 0.0710 | 0.024* | |
H12B | 0.2794 | 0.8131 | 0.1232 | 0.024* | |
C13 | 0.17749 (13) | 0.78028 (17) | 0.15563 (12) | 0.0191 (5) | |
H13A | 0.1454 | 0.8289 | 0.1272 | 0.023* | |
H13B | 0.1466 | 0.7220 | 0.1594 | 0.023* | |
O14 | 0.20647 (9) | 0.81722 (12) | 0.22479 (9) | 0.0196 (3) | |
C15 | 0.15707 (12) | 0.84805 (16) | 0.26797 (12) | 0.0159 (4) | |
C16 | 0.07835 (13) | 0.83922 (17) | 0.25266 (13) | 0.0196 (5) | |
H16 | 0.0549 | 0.8126 | 0.2087 | 0.024* | |
C17 | 0.03439 (13) | 0.86984 (17) | 0.30238 (14) | 0.0213 (5) | |
H17 | −0.0193 | 0.8631 | 0.2923 | 0.026* | |
C18 | 0.06749 (13) | 0.91003 (16) | 0.36636 (13) | 0.0199 (5) | |
H18 | 0.0369 | 0.9297 | 0.4003 | 0.024* | |
C19 | 0.14625 (13) | 0.92140 (16) | 0.38051 (12) | 0.0161 (4) | |
H19 | 0.1691 | 0.9504 | 0.4238 | 0.019* | |
C20 | 0.19172 (12) | 0.89076 (15) | 0.33195 (11) | 0.0139 (4) | |
C21 | 0.27704 (12) | 0.89994 (15) | 0.34368 (11) | 0.0121 (4) | |
H21 | 0.2925 | 0.9099 | 0.2960 | 0.014* | |
N22 | 0.30377 (10) | 0.98427 (13) | 0.38774 (10) | 0.0135 (4) | |
H22N | 0.2765 | 1.0389 | 0.3853 | 0.016* | |
C23 | 0.37559 (12) | 0.99051 (15) | 0.42276 (11) | 0.0123 (4) | |
N24 | 0.42203 (10) | 0.91516 (13) | 0.41981 (10) | 0.0134 (4) | |
H24N | 0.4688 | 0.9169 | 0.4458 | 0.016* | |
N25 | 0.31621 (10) | 0.81396 (13) | 0.37458 (9) | 0.0117 (3) | |
C26 | 0.30034 (12) | 0.79035 (16) | 0.44608 (11) | 0.0153 (4) | |
H26A | 0.2453 | 0.7853 | 0.4448 | 0.023* | |
H26B | 0.3207 | 0.8411 | 0.4794 | 0.023* | |
H26C | 0.3244 | 0.7290 | 0.4616 | 0.023* | |
S2 | 0.59769 (3) | 0.40566 (4) | 0.02497 (3) | 0.01375 (12) | |
C27 | 0.59706 (11) | 0.65460 (15) | 0.13409 (11) | 0.0124 (4) | |
H27 | 0.5841 | 0.6334 | 0.1808 | 0.015* | |
C28 | 0.55282 (12) | 0.74494 (15) | 0.11245 (13) | 0.0157 (4) | |
C29 | 0.52331 (13) | 0.76760 (17) | 0.04246 (14) | 0.0212 (5) | |
H29 | 0.5288 | 0.7232 | 0.0058 | 0.025* | |
C30 | 0.48566 (15) | 0.85456 (19) | 0.02499 (16) | 0.0306 (6) | |
H30 | 0.4660 | 0.8692 | −0.0231 | 0.037* | |
C31 | 0.47739 (16) | 0.91880 (19) | 0.07820 (17) | 0.0341 (7) | |
H31 | 0.4516 | 0.9778 | 0.0665 | 0.041* | |
C32 | 0.50645 (14) | 0.89852 (18) | 0.14926 (16) | 0.0286 (6) | |
H32 | 0.5003 | 0.9432 | 0.1856 | 0.034* | |
C33 | 0.54468 (13) | 0.81189 (17) | 0.16622 (13) | 0.0197 (5) | |
O34 | 0.57591 (10) | 0.78517 (12) | 0.23351 (9) | 0.0225 (4) | |
C35 | 0.58146 (14) | 0.85641 (18) | 0.28819 (14) | 0.0245 (5) | |
H35A | 0.5302 | 0.8747 | 0.2971 | 0.029* | |
H35B | 0.6069 | 0.9146 | 0.2736 | 0.029* | |
C36 | 0.62663 (15) | 0.81447 (19) | 0.35413 (14) | 0.0268 (6) | |
H36A | 0.6216 | 0.8554 | 0.3956 | 0.032* | |
H36B | 0.6072 | 0.7496 | 0.3628 | 0.032* | |
O37 | 0.70496 (10) | 0.80853 (13) | 0.34550 (9) | 0.0231 (4) | |
C38 | 0.74684 (16) | 0.73886 (19) | 0.39038 (13) | 0.0272 (6) | |
H38A | 0.7145 | 0.6822 | 0.3953 | 0.033* | |
H38B | 0.7636 | 0.7664 | 0.4382 | 0.033* | |
C39 | 0.81451 (15) | 0.70940 (18) | 0.35800 (13) | 0.0256 (5) | |
H39A | 0.8420 | 0.7668 | 0.3449 | 0.031* | |
H39B | 0.8497 | 0.6705 | 0.3922 | 0.031* | |
O40 | 0.78678 (10) | 0.65387 (12) | 0.29591 (9) | 0.0222 (4) | |
C41 | 0.83531 (13) | 0.63239 (16) | 0.24964 (13) | 0.0188 (5) | |
C42 | 0.91393 (14) | 0.64661 (18) | 0.26350 (15) | 0.0267 (6) | |
H42 | 0.9373 | 0.6719 | 0.3080 | 0.032* | |
C43 | 0.95744 (14) | 0.62359 (19) | 0.21210 (17) | 0.0301 (6) | |
H43 | 1.0107 | 0.6344 | 0.2215 | 0.036* | |
C44 | 0.92544 (14) | 0.58514 (18) | 0.14725 (15) | 0.0259 (6) | |
H44 | 0.9562 | 0.5701 | 0.1124 | 0.031* | |
C45 | 0.84693 (13) | 0.56877 (16) | 0.13378 (13) | 0.0191 (5) | |
H45 | 0.8244 | 0.5412 | 0.0898 | 0.023* | |
C46 | 0.80152 (12) | 0.59253 (16) | 0.18437 (12) | 0.0151 (4) | |
C47 | 0.71614 (12) | 0.58252 (15) | 0.17053 (11) | 0.0125 (4) | |
H47 | 0.6992 | 0.5673 | 0.2168 | 0.015* | |
N48 | 0.69185 (10) | 0.50260 (13) | 0.12106 (10) | 0.0137 (4) | |
H48N | 0.7213 | 0.4497 | 0.1260 | 0.016* | |
C49 | 0.62317 (12) | 0.50040 (15) | 0.07968 (11) | 0.0119 (4) | |
N50 | 0.57641 (10) | 0.57561 (13) | 0.08247 (10) | 0.0134 (4) | |
H50N | 0.5309 | 0.5738 | 0.0542 | 0.016* | |
N51 | 0.67883 (10) | 0.67119 (13) | 0.14366 (9) | 0.0120 (3) | |
C52 | 0.70353 (12) | 0.70762 (16) | 0.07863 (11) | 0.0153 (4) | |
H52A | 0.7585 | 0.7190 | 0.0877 | 0.023* | |
H52B | 0.6771 | 0.7680 | 0.0644 | 0.023* | |
H52C | 0.6915 | 0.6602 | 0.0405 | 0.023* | |
Cl1 | 0.27961 (4) | 0.53821 (5) | 0.38281 (5) | 0.0428 (2) | |
Cl2 | 0.14136 (4) | 0.64065 (5) | 0.40015 (4) | 0.03496 (17) | |
Cl3 | 0.16124 (4) | 0.56818 (5) | 0.26278 (4) | 0.03620 (17) | |
C53 | 0.20805 (15) | 0.61681 (19) | 0.34302 (14) | 0.0251 (5) | |
H53 | 0.2322 | 0.6788 | 0.3324 | 0.030* | |
Cl4 | 0.88331 (5) | 0.85664 (6) | 0.13270 (5) | 0.0476 (2) | |
Cl5 | 0.75321 (6) | 0.96817 (6) | 0.06923 (4) | 0.0536 (2) | |
Cl6 | 0.75812 (5) | 0.88555 (5) | 0.21014 (4) | 0.03796 (18) | |
C54 | 0.8111 (2) | 0.9377 (2) | 0.14904 (15) | 0.0376 (7) | |
H54 | 0.8358 | 0.9976 | 0.1707 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0143 (2) | 0.0117 (2) | 0.0157 (3) | −0.00020 (19) | −0.00189 (19) | −0.00450 (19) |
C1 | 0.0114 (9) | 0.0128 (10) | 0.0124 (10) | −0.0010 (8) | 0.0013 (8) | −0.0047 (8) |
C2 | 0.0109 (9) | 0.0134 (10) | 0.0175 (10) | −0.0011 (8) | 0.0017 (8) | −0.0029 (8) |
C3 | 0.0160 (10) | 0.0150 (10) | 0.0186 (11) | −0.0028 (8) | 0.0002 (8) | −0.0024 (8) |
C4 | 0.0211 (11) | 0.0199 (12) | 0.0247 (12) | −0.0003 (9) | −0.0044 (9) | 0.0019 (9) |
C5 | 0.0211 (12) | 0.0141 (11) | 0.0361 (14) | 0.0041 (9) | 0.0021 (10) | 0.0009 (10) |
C6 | 0.0196 (11) | 0.0157 (11) | 0.0273 (13) | 0.0029 (9) | 0.0017 (9) | −0.0050 (9) |
C7 | 0.0129 (10) | 0.0152 (10) | 0.0201 (11) | −0.0004 (8) | 0.0022 (8) | −0.0031 (8) |
O8 | 0.0214 (8) | 0.0183 (8) | 0.0162 (8) | 0.0037 (6) | −0.0013 (6) | −0.0087 (6) |
C9 | 0.0180 (11) | 0.0196 (11) | 0.0184 (11) | −0.0006 (9) | 0.0045 (9) | −0.0096 (9) |
C10 | 0.0188 (11) | 0.0243 (12) | 0.0171 (11) | −0.0029 (9) | 0.0068 (9) | −0.0061 (9) |
O11 | 0.0164 (8) | 0.0196 (8) | 0.0182 (8) | −0.0022 (6) | 0.0041 (6) | −0.0017 (6) |
C12 | 0.0251 (12) | 0.0216 (12) | 0.0136 (11) | −0.0026 (9) | 0.0020 (9) | −0.0023 (9) |
C13 | 0.0187 (11) | 0.0212 (11) | 0.0149 (11) | −0.0016 (9) | −0.0047 (9) | −0.0059 (9) |
O14 | 0.0135 (7) | 0.0263 (9) | 0.0178 (8) | −0.0010 (7) | −0.0007 (6) | −0.0107 (7) |
C15 | 0.0140 (10) | 0.0141 (10) | 0.0190 (11) | 0.0003 (8) | 0.0012 (8) | −0.0024 (8) |
C16 | 0.0150 (11) | 0.0162 (11) | 0.0252 (12) | −0.0019 (9) | −0.0042 (9) | −0.0028 (9) |
C17 | 0.0121 (10) | 0.0179 (11) | 0.0333 (13) | −0.0013 (9) | 0.0019 (9) | 0.0008 (10) |
C18 | 0.0173 (11) | 0.0157 (11) | 0.0280 (13) | 0.0014 (9) | 0.0075 (9) | 0.0030 (9) |
C19 | 0.0175 (11) | 0.0134 (10) | 0.0180 (11) | 0.0012 (8) | 0.0044 (8) | 0.0007 (8) |
C20 | 0.0136 (10) | 0.0116 (10) | 0.0160 (10) | 0.0004 (8) | 0.0007 (8) | −0.0002 (8) |
C21 | 0.0123 (10) | 0.0123 (10) | 0.0113 (9) | −0.0005 (8) | 0.0010 (7) | −0.0033 (8) |
N22 | 0.0119 (8) | 0.0113 (8) | 0.0161 (9) | 0.0010 (7) | −0.0013 (7) | −0.0026 (7) |
C23 | 0.0146 (10) | 0.0122 (10) | 0.0102 (9) | −0.0008 (8) | 0.0028 (8) | −0.0009 (7) |
N24 | 0.0104 (8) | 0.0116 (8) | 0.0171 (9) | −0.0004 (7) | −0.0009 (7) | −0.0046 (7) |
N25 | 0.0097 (8) | 0.0131 (8) | 0.0128 (8) | −0.0015 (7) | 0.0032 (7) | −0.0021 (7) |
C26 | 0.0154 (10) | 0.0164 (10) | 0.0148 (10) | −0.0012 (8) | 0.0043 (8) | 0.0010 (8) |
S2 | 0.0152 (2) | 0.0117 (2) | 0.0135 (2) | 0.00074 (19) | −0.00027 (19) | −0.00370 (19) |
C27 | 0.0112 (9) | 0.0130 (10) | 0.0130 (10) | −0.0016 (8) | 0.0023 (8) | −0.0030 (8) |
C28 | 0.0099 (9) | 0.0111 (10) | 0.0260 (12) | −0.0013 (8) | 0.0024 (8) | −0.0041 (8) |
C29 | 0.0177 (11) | 0.0147 (11) | 0.0282 (13) | −0.0010 (9) | −0.0051 (9) | −0.0033 (9) |
C30 | 0.0281 (13) | 0.0183 (12) | 0.0397 (16) | 0.0009 (10) | −0.0117 (12) | −0.0004 (11) |
C31 | 0.0262 (14) | 0.0180 (13) | 0.0537 (19) | 0.0066 (10) | −0.0072 (13) | −0.0032 (12) |
C32 | 0.0216 (12) | 0.0161 (12) | 0.0479 (17) | 0.0024 (10) | 0.0053 (11) | −0.0126 (11) |
C33 | 0.0147 (10) | 0.0152 (11) | 0.0291 (13) | −0.0023 (9) | 0.0031 (9) | −0.0058 (9) |
O34 | 0.0267 (9) | 0.0186 (8) | 0.0231 (9) | −0.0029 (7) | 0.0072 (7) | −0.0111 (7) |
C35 | 0.0234 (12) | 0.0234 (12) | 0.0296 (13) | −0.0075 (10) | 0.0131 (10) | −0.0164 (10) |
C36 | 0.0314 (14) | 0.0287 (13) | 0.0246 (13) | −0.0110 (11) | 0.0172 (11) | −0.0119 (10) |
O37 | 0.0280 (9) | 0.0235 (9) | 0.0193 (9) | −0.0071 (7) | 0.0083 (7) | −0.0028 (7) |
C38 | 0.0424 (15) | 0.0241 (13) | 0.0146 (11) | −0.0111 (11) | 0.0027 (10) | −0.0033 (9) |
C39 | 0.0319 (14) | 0.0224 (12) | 0.0187 (12) | −0.0057 (10) | −0.0080 (10) | −0.0051 (9) |
O40 | 0.0229 (8) | 0.0233 (9) | 0.0179 (8) | −0.0044 (7) | −0.0041 (7) | −0.0079 (7) |
C41 | 0.0169 (11) | 0.0122 (10) | 0.0251 (12) | −0.0002 (8) | −0.0028 (9) | 0.0022 (9) |
C42 | 0.0178 (12) | 0.0196 (12) | 0.0376 (15) | −0.0043 (9) | −0.0107 (10) | 0.0001 (10) |
C43 | 0.0131 (11) | 0.0193 (12) | 0.0562 (18) | −0.0022 (9) | −0.0001 (11) | 0.0079 (12) |
C44 | 0.0172 (11) | 0.0195 (12) | 0.0425 (16) | 0.0035 (9) | 0.0091 (11) | 0.0100 (11) |
C45 | 0.0182 (11) | 0.0143 (10) | 0.0254 (12) | 0.0029 (9) | 0.0052 (9) | 0.0045 (9) |
C46 | 0.0123 (10) | 0.0133 (10) | 0.0187 (11) | −0.0007 (8) | −0.0008 (8) | 0.0026 (8) |
C47 | 0.0131 (10) | 0.0128 (10) | 0.0112 (9) | −0.0015 (8) | 0.0010 (8) | −0.0008 (7) |
N48 | 0.0125 (8) | 0.0113 (8) | 0.0161 (9) | 0.0017 (7) | −0.0013 (7) | −0.0030 (7) |
C49 | 0.0138 (10) | 0.0115 (10) | 0.0109 (9) | −0.0008 (8) | 0.0036 (8) | 0.0003 (7) |
N50 | 0.0111 (8) | 0.0113 (8) | 0.0170 (9) | −0.0005 (7) | −0.0003 (7) | −0.0036 (7) |
N51 | 0.0107 (8) | 0.0123 (8) | 0.0132 (8) | −0.0002 (7) | 0.0022 (7) | −0.0010 (7) |
C52 | 0.0157 (10) | 0.0165 (10) | 0.0145 (10) | −0.0031 (8) | 0.0052 (8) | 0.0011 (8) |
Cl1 | 0.0397 (4) | 0.0301 (4) | 0.0545 (5) | 0.0058 (3) | −0.0050 (3) | −0.0007 (3) |
Cl2 | 0.0377 (4) | 0.0322 (4) | 0.0395 (4) | −0.0119 (3) | 0.0199 (3) | −0.0109 (3) |
Cl3 | 0.0401 (4) | 0.0346 (4) | 0.0326 (4) | 0.0027 (3) | 0.0016 (3) | −0.0125 (3) |
C53 | 0.0251 (12) | 0.0216 (12) | 0.0295 (13) | −0.0012 (10) | 0.0066 (10) | −0.0038 (10) |
Cl4 | 0.0415 (4) | 0.0501 (5) | 0.0533 (5) | −0.0164 (4) | 0.0138 (4) | 0.0021 (4) |
Cl5 | 0.0888 (7) | 0.0322 (4) | 0.0354 (4) | −0.0030 (4) | −0.0036 (4) | 0.0029 (3) |
Cl6 | 0.0564 (5) | 0.0309 (4) | 0.0299 (4) | −0.0131 (3) | 0.0171 (3) | −0.0072 (3) |
C54 | 0.061 (2) | 0.0286 (14) | 0.0242 (14) | −0.0185 (14) | 0.0108 (13) | −0.0036 (11) |
S1—C23 | 1.700 (2) | C27—H27 | 1.0000 |
C1—N25 | 1.467 (3) | C28—C29 | 1.389 (3) |
C1—N24 | 1.482 (3) | C28—C33 | 1.410 (3) |
C1—C2 | 1.503 (3) | C29—C30 | 1.398 (3) |
C1—H1 | 1.0000 | C29—H29 | 0.9500 |
C2—C3 | 1.391 (3) | C30—C31 | 1.377 (4) |
C2—C7 | 1.409 (3) | C30—H30 | 0.9500 |
C3—C4 | 1.395 (3) | C31—C32 | 1.399 (4) |
C3—H3 | 0.9500 | C31—H31 | 0.9500 |
C4—C5 | 1.387 (4) | C32—C33 | 1.397 (3) |
C4—H4 | 0.9500 | C32—H32 | 0.9500 |
C5—C6 | 1.392 (4) | C33—O34 | 1.365 (3) |
C5—H5 | 0.9500 | O34—C35 | 1.430 (3) |
C6—C7 | 1.398 (3) | C35—C36 | 1.498 (4) |
C6—H6 | 0.9500 | C35—H35A | 0.9900 |
C7—O8 | 1.363 (3) | C35—H35B | 0.9900 |
O8—C9 | 1.434 (3) | C36—O37 | 1.435 (3) |
C9—C10 | 1.498 (3) | C36—H36A | 0.9900 |
C9—H9A | 0.9900 | C36—H36B | 0.9900 |
C9—H9B | 0.9900 | O37—C38 | 1.423 (3) |
C10—O11 | 1.433 (3) | C38—C39 | 1.498 (4) |
C10—H10A | 0.9900 | C38—H38A | 0.9900 |
C10—H10B | 0.9900 | C38—H38B | 0.9900 |
O11—C12 | 1.427 (3) | C39—O40 | 1.433 (3) |
C12—C13 | 1.503 (3) | C39—H39A | 0.9900 |
C12—H12A | 0.9900 | C39—H39B | 0.9900 |
C12—H12B | 0.9900 | O40—C41 | 1.364 (3) |
C13—O14 | 1.432 (3) | C41—C42 | 1.399 (3) |
C13—H13A | 0.9900 | C41—C46 | 1.406 (3) |
C13—H13B | 0.9900 | C42—C43 | 1.381 (4) |
O14—C15 | 1.367 (3) | C42—H42 | 0.9500 |
C15—C16 | 1.393 (3) | C43—C44 | 1.383 (4) |
C15—C20 | 1.407 (3) | C43—H43 | 0.9500 |
C16—C17 | 1.390 (3) | C44—C45 | 1.401 (3) |
C16—H16 | 0.9500 | C44—H44 | 0.9500 |
C17—C18 | 1.385 (4) | C45—C46 | 1.395 (3) |
C17—H17 | 0.9500 | C45—H45 | 0.9500 |
C18—C19 | 1.396 (3) | C46—C47 | 1.510 (3) |
C18—H18 | 0.9500 | C47—N51 | 1.456 (3) |
C19—C20 | 1.392 (3) | C47—N48 | 1.477 (3) |
C19—H19 | 0.9500 | C47—H47 | 1.0000 |
C20—C21 | 1.508 (3) | N48—C49 | 1.347 (3) |
C21—N25 | 1.461 (3) | N48—H48N | 0.9000 |
C21—N22 | 1.477 (3) | C49—N50 | 1.345 (3) |
C21—H21 | 1.0000 | N50—H50N | 0.9000 |
N22—C23 | 1.349 (3) | N51—C52 | 1.470 (3) |
N22—H22N | 0.9000 | C52—H52A | 0.9800 |
C23—N24 | 1.343 (3) | C52—H52B | 0.9800 |
N24—H24N | 0.9000 | C52—H52C | 0.9800 |
N25—C26 | 1.472 (3) | Cl1—C53 | 1.758 (3) |
C26—H26A | 0.9800 | Cl2—C53 | 1.768 (3) |
C26—H26B | 0.9800 | Cl3—C53 | 1.756 (3) |
C26—H26C | 0.9800 | C53—H53 | 1.0000 |
S2—C49 | 1.697 (2) | Cl4—C54 | 1.777 (4) |
C27—N51 | 1.459 (3) | Cl5—C54 | 1.748 (3) |
C27—N50 | 1.482 (3) | Cl6—C54 | 1.769 (3) |
C27—C28 | 1.506 (3) | C54—H54 | 1.0000 |
N25—C1—N24 | 109.05 (16) | C29—C28—C33 | 118.7 (2) |
N25—C1—C2 | 112.06 (17) | C29—C28—C27 | 123.6 (2) |
N24—C1—C2 | 113.05 (17) | C33—C28—C27 | 117.6 (2) |
N25—C1—H1 | 107.5 | C28—C29—C30 | 121.2 (2) |
N24—C1—H1 | 107.5 | C28—C29—H29 | 119.4 |
C2—C1—H1 | 107.5 | C30—C29—H29 | 119.4 |
C3—C2—C7 | 119.0 (2) | C31—C30—C29 | 119.4 (3) |
C3—C2—C1 | 124.00 (19) | C31—C30—H30 | 120.3 |
C7—C2—C1 | 116.96 (19) | C29—C30—H30 | 120.3 |
C2—C3—C4 | 120.9 (2) | C30—C31—C32 | 121.0 (2) |
C2—C3—H3 | 119.5 | C30—C31—H31 | 119.5 |
C4—C3—H3 | 119.5 | C32—C31—H31 | 119.5 |
C5—C4—C3 | 119.5 (2) | C33—C32—C31 | 119.3 (2) |
C5—C4—H4 | 120.2 | C33—C32—H32 | 120.4 |
C3—C4—H4 | 120.2 | C31—C32—H32 | 120.4 |
C4—C5—C6 | 120.9 (2) | O34—C33—C32 | 124.2 (2) |
C4—C5—H5 | 119.6 | O34—C33—C28 | 115.4 (2) |
C6—C5—H5 | 119.6 | C32—C33—C28 | 120.4 (2) |
C5—C6—C7 | 119.4 (2) | C33—O34—C35 | 117.75 (19) |
C5—C6—H6 | 120.3 | O34—C35—C36 | 107.8 (2) |
C7—C6—H6 | 120.3 | O34—C35—H35A | 110.1 |
O8—C7—C6 | 124.6 (2) | C36—C35—H35A | 110.1 |
O8—C7—C2 | 115.06 (19) | O34—C35—H35B | 110.1 |
C6—C7—C2 | 120.3 (2) | C36—C35—H35B | 110.1 |
C7—O8—C9 | 118.62 (18) | H35A—C35—H35B | 108.5 |
O8—C9—C10 | 107.44 (19) | O37—C36—C35 | 109.2 (2) |
O8—C9—H9A | 110.2 | O37—C36—H36A | 109.8 |
C10—C9—H9A | 110.2 | C35—C36—H36A | 109.8 |
O8—C9—H9B | 110.2 | O37—C36—H36B | 109.8 |
C10—C9—H9B | 110.2 | C35—C36—H36B | 109.8 |
H9A—C9—H9B | 108.5 | H36A—C36—H36B | 108.3 |
O11—C10—C9 | 109.46 (18) | C38—O37—C36 | 113.41 (19) |
O11—C10—H10A | 109.8 | O37—C38—C39 | 108.6 (2) |
C9—C10—H10A | 109.8 | O37—C38—H38A | 110.0 |
O11—C10—H10B | 109.8 | C39—C38—H38A | 110.0 |
C9—C10—H10B | 109.8 | O37—C38—H38B | 110.0 |
H10A—C10—H10B | 108.2 | C39—C38—H38B | 110.0 |
C12—O11—C10 | 114.08 (18) | H38A—C38—H38B | 108.4 |
O11—C12—C13 | 108.74 (19) | O40—C39—C38 | 107.1 (2) |
O11—C12—H12A | 109.9 | O40—C39—H39A | 110.3 |
C13—C12—H12A | 109.9 | C38—C39—H39A | 110.3 |
O11—C12—H12B | 109.9 | O40—C39—H39B | 110.3 |
C13—C12—H12B | 109.9 | C38—C39—H39B | 110.3 |
H12A—C12—H12B | 108.3 | H39A—C39—H39B | 108.6 |
O14—C13—C12 | 106.28 (18) | C41—O40—C39 | 118.75 (19) |
O14—C13—H13A | 110.5 | O40—C41—C42 | 124.6 (2) |
C12—C13—H13A | 110.5 | O40—C41—C46 | 115.6 (2) |
O14—C13—H13B | 110.5 | C42—C41—C46 | 119.8 (2) |
C12—C13—H13B | 110.5 | C43—C42—C41 | 119.6 (2) |
H13A—C13—H13B | 108.7 | C43—C42—H42 | 120.2 |
C15—O14—C13 | 119.62 (17) | C41—C42—H42 | 120.2 |
O14—C15—C16 | 124.8 (2) | C42—C43—C44 | 121.7 (2) |
O14—C15—C20 | 114.71 (19) | C42—C43—H43 | 119.2 |
C16—C15—C20 | 120.4 (2) | C44—C43—H43 | 119.2 |
C17—C16—C15 | 119.3 (2) | C43—C44—C45 | 118.9 (2) |
C17—C16—H16 | 120.3 | C43—C44—H44 | 120.5 |
C15—C16—H16 | 120.3 | C45—C44—H44 | 120.5 |
C18—C17—C16 | 121.1 (2) | C46—C45—C44 | 120.6 (2) |
C18—C17—H17 | 119.5 | C46—C45—H45 | 119.7 |
C16—C17—H17 | 119.5 | C44—C45—H45 | 119.7 |
C17—C18—C19 | 119.3 (2) | C45—C46—C41 | 119.4 (2) |
C17—C18—H18 | 120.3 | C45—C46—C47 | 122.6 (2) |
C19—C18—H18 | 120.3 | C41—C46—C47 | 117.9 (2) |
C20—C19—C18 | 120.8 (2) | N51—C47—N48 | 110.06 (16) |
C20—C19—H19 | 119.6 | N51—C47—C46 | 112.00 (17) |
C18—C19—H19 | 119.6 | N48—C47—C46 | 111.42 (17) |
C19—C20—C15 | 118.9 (2) | N51—C47—H47 | 107.7 |
C19—C20—C21 | 123.9 (2) | N48—C47—H47 | 107.7 |
C15—C20—C21 | 117.19 (19) | C46—C47—H47 | 107.7 |
N25—C21—N22 | 109.38 (16) | C49—N48—C47 | 122.48 (18) |
N25—C21—C20 | 113.35 (17) | C49—N48—H48N | 120.2 |
N22—C21—C20 | 112.20 (17) | C47—N48—H48N | 116.3 |
N25—C21—H21 | 107.2 | N50—C49—N48 | 118.09 (19) |
N22—C21—H21 | 107.2 | N50—C49—S2 | 121.49 (16) |
C20—C21—H21 | 107.2 | N48—C49—S2 | 120.42 (16) |
C23—N22—C21 | 121.79 (18) | C49—N50—C27 | 120.93 (17) |
C23—N22—H22N | 115.8 | C49—N50—H50N | 117.5 |
C21—N22—H22N | 121.2 | C27—N50—H50N | 121.5 |
N24—C23—N22 | 118.18 (19) | C47—N51—C27 | 107.53 (16) |
N24—C23—S1 | 121.67 (16) | C47—N51—C52 | 114.02 (17) |
N22—C23—S1 | 120.15 (16) | C27—N51—C52 | 112.19 (17) |
C23—N24—C1 | 120.96 (17) | N51—C52—H52A | 109.5 |
C23—N24—H24N | 118.7 | N51—C52—H52B | 109.5 |
C1—N24—H24N | 120.4 | H52A—C52—H52B | 109.5 |
C21—N25—C1 | 105.98 (16) | N51—C52—H52C | 109.5 |
C21—N25—C26 | 113.91 (16) | H52A—C52—H52C | 109.5 |
C1—N25—C26 | 112.00 (17) | H52B—C52—H52C | 109.5 |
N25—C26—H26A | 109.5 | Cl3—C53—Cl1 | 110.29 (14) |
N25—C26—H26B | 109.5 | Cl3—C53—Cl2 | 109.61 (14) |
H26A—C26—H26B | 109.5 | Cl1—C53—Cl2 | 111.40 (15) |
N25—C26—H26C | 109.5 | Cl3—C53—H53 | 108.5 |
H26A—C26—H26C | 109.5 | Cl1—C53—H53 | 108.5 |
H26B—C26—H26C | 109.5 | Cl2—C53—H53 | 108.5 |
N51—C27—N50 | 109.73 (16) | Cl5—C54—Cl6 | 111.66 (19) |
N51—C27—C28 | 111.81 (17) | Cl5—C54—Cl4 | 110.18 (16) |
N50—C27—C28 | 111.95 (17) | Cl6—C54—Cl4 | 109.46 (17) |
N51—C27—H27 | 107.7 | Cl5—C54—H54 | 108.5 |
N50—C27—H27 | 107.7 | Cl6—C54—H54 | 108.5 |
C28—C27—H27 | 107.7 | Cl4—C54—H54 | 108.5 |
N25—C1—C2—C3 | −96.0 (2) | N51—C27—C28—C29 | 97.1 (2) |
N24—C1—C2—C3 | 27.8 (3) | N50—C27—C28—C29 | −26.5 (3) |
N25—C1—C2—C7 | 81.0 (2) | N51—C27—C28—C33 | −79.5 (2) |
N24—C1—C2—C7 | −155.28 (19) | N50—C27—C28—C33 | 156.93 (19) |
C7—C2—C3—C4 | 1.6 (3) | C33—C28—C29—C30 | −0.5 (3) |
C1—C2—C3—C4 | 178.5 (2) | C27—C28—C29—C30 | −177.0 (2) |
C2—C3—C4—C5 | −1.1 (4) | C28—C29—C30—C31 | −0.3 (4) |
C3—C4—C5—C6 | 0.3 (4) | C29—C30—C31—C32 | 0.4 (4) |
C4—C5—C6—C7 | −0.1 (4) | C30—C31—C32—C33 | 0.3 (4) |
C5—C6—C7—O8 | −179.8 (2) | C31—C32—C33—O34 | 179.3 (2) |
C5—C6—C7—C2 | 0.6 (4) | C31—C32—C33—C28 | −1.0 (4) |
C3—C2—C7—O8 | 178.99 (19) | C29—C28—C33—O34 | −179.2 (2) |
C1—C2—C7—O8 | 1.9 (3) | C27—C28—C33—O34 | −2.4 (3) |
C3—C2—C7—C6 | −1.4 (3) | C29—C28—C33—C32 | 1.1 (3) |
C1—C2—C7—C6 | −178.5 (2) | C27—C28—C33—C32 | 177.9 (2) |
C6—C7—O8—C9 | 1.3 (3) | C32—C33—O34—C35 | −11.2 (3) |
C2—C7—O8—C9 | −179.07 (19) | C28—C33—O34—C35 | 169.1 (2) |
C7—O8—C9—C10 | −176.94 (19) | C33—O34—C35—C36 | −172.36 (19) |
O8—C9—C10—O11 | −71.7 (2) | O34—C35—C36—O37 | 72.6 (2) |
C9—C10—O11—C12 | 150.54 (19) | C35—C36—O37—C38 | −157.19 (19) |
C10—O11—C12—C13 | −154.40 (18) | C36—O37—C38—C39 | 156.84 (19) |
O11—C12—C13—O14 | 67.2 (2) | O37—C38—C39—O40 | −70.6 (2) |
C12—C13—O14—C15 | 177.99 (19) | C38—C39—O40—C41 | 168.6 (2) |
C13—O14—C15—C16 | 5.8 (3) | C39—O40—C41—C42 | 11.1 (3) |
C13—O14—C15—C20 | −174.6 (2) | C39—O40—C41—C46 | −169.4 (2) |
O14—C15—C16—C17 | 177.3 (2) | O40—C41—C42—C43 | −179.0 (2) |
C20—C15—C16—C17 | −2.3 (3) | C46—C41—C42—C43 | 1.7 (4) |
C15—C16—C17—C18 | 0.9 (4) | C41—C42—C43—C44 | −1.1 (4) |
C16—C17—C18—C19 | 1.1 (4) | C42—C43—C44—C45 | −0.4 (4) |
C17—C18—C19—C20 | −1.6 (3) | C43—C44—C45—C46 | 1.2 (4) |
C18—C19—C20—C15 | 0.1 (3) | C44—C45—C46—C41 | −0.6 (3) |
C18—C19—C20—C21 | −179.6 (2) | C44—C45—C46—C47 | 175.8 (2) |
O14—C15—C20—C19 | −177.8 (2) | O40—C41—C46—C45 | 179.7 (2) |
C16—C15—C20—C19 | 1.9 (3) | C42—C41—C46—C45 | −0.8 (3) |
O14—C15—C20—C21 | 1.9 (3) | O40—C41—C46—C47 | 3.2 (3) |
C16—C15—C20—C21 | −178.4 (2) | C42—C41—C46—C47 | −177.4 (2) |
C19—C20—C21—N25 | 94.1 (2) | C45—C46—C47—N51 | −92.9 (2) |
C15—C20—C21—N25 | −85.6 (2) | C41—C46—C47—N51 | 83.6 (2) |
C19—C20—C21—N22 | −30.4 (3) | C45—C46—C47—N48 | 30.9 (3) |
C15—C20—C21—N22 | 149.90 (19) | C41—C46—C47—N48 | −152.65 (19) |
N25—C21—N22—C23 | 32.5 (3) | N51—C47—N48—C49 | −29.1 (3) |
C20—C21—N22—C23 | 159.19 (19) | C46—C47—N48—C49 | −153.96 (19) |
C21—N22—C23—N24 | −3.5 (3) | C47—N48—C49—N50 | 2.0 (3) |
C21—N22—C23—S1 | 177.20 (15) | C47—N48—C49—S2 | −178.82 (15) |
N22—C23—N24—C1 | 5.2 (3) | N48—C49—N50—C27 | −5.3 (3) |
S1—C23—N24—C1 | −175.49 (15) | S2—C49—N50—C27 | 175.63 (15) |
N25—C1—N24—C23 | −35.7 (3) | N51—C27—N50—C49 | 35.3 (3) |
C2—C1—N24—C23 | −161.11 (19) | C28—C27—N50—C49 | 160.02 (19) |
N22—C21—N25—C1 | −60.5 (2) | N48—C47—N51—C27 | 57.0 (2) |
C20—C21—N25—C1 | 173.45 (17) | C46—C47—N51—C27 | −178.42 (17) |
N22—C21—N25—C26 | 63.1 (2) | N48—C47—N51—C52 | −68.0 (2) |
C20—C21—N25—C26 | −63.0 (2) | C46—C47—N51—C52 | 56.5 (2) |
N24—C1—N25—C21 | 62.2 (2) | N50—C27—N51—C47 | −60.2 (2) |
C2—C1—N25—C21 | −171.87 (17) | C28—C27—N51—C47 | 174.96 (17) |
N24—C1—N25—C26 | −62.6 (2) | N50—C27—N51—C52 | 66.0 (2) |
C2—C1—N25—C26 | 63.3 (2) | C28—C27—N51—C52 | −58.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N22—H22N···O11i | 0.90 | 2.32 | 3.183 (2) | 161 |
N24—H24N···S1ii | 0.90 | 2.55 | 3.445 (2) | 173 |
N48—H48N···O37iii | 0.90 | 2.38 | 3.273 (3) | 172 |
N50—H50N···S2iv | 0.90 | 2.55 | 3.445 (2) | 172 |
C10—H10B···S2iv | 0.99 | 2.80 | 3.747 (2) | 160 |
C21—H21···Cl3i | 1.00 | 2.66 | 3.395 (2) | 130 |
C26—H26A···Cl2 | 0.98 | 2.78 | 3.514 (2) | 133 |
C36—H36A···S1ii | 0.99 | 2.78 | 3.729 (3) | 160 |
C43—H43···Cl3v | 0.95 | 2.83 | 3.690 (3) | 151 |
C53—H53···N25 | 1.00 | 2.46 | 3.353 (3) | 149 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1, −y+2, −z+1; (iii) −x+3/2, y−1/2, −z+1/2; (iv) −x+1, −y+1, −z; (v) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C20H23N3O3S·CHCl3 |
Mr | 504.84 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 17.8370 (5), 13.9173 (4), 19.0561 (6) |
β (°) | 99.222 (1) |
V (Å3) | 4669.4 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.51 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.862, 0.905 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 52534, 11281, 8711 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.145, 1.00 |
No. of reflections | 11281 |
No. of parameters | 561 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.38, −1.05 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N22—H22N···O11i | 0.90 | 2.32 | 3.183 (2) | 161 |
N24—H24N···S1ii | 0.90 | 2.55 | 3.445 (2) | 173 |
N48—H48N···O37iii | 0.90 | 2.38 | 3.273 (3) | 172 |
N50—H50N···S2iv | 0.90 | 2.55 | 3.445 (2) | 172 |
C10—H10B···S2iv | 0.99 | 2.80 | 3.747 (2) | 160 |
C21—H21···Cl3i | 1.00 | 2.66 | 3.395 (2) | 130 |
C26—H26A···Cl2 | 0.98 | 2.78 | 3.514 (2) | 133 |
C36—H36A···S1ii | 0.99 | 2.78 | 3.729 (3) | 160 |
C43—H43···Cl3v | 0.95 | 2.83 | 3.690 (3) | 151 |
C53—H53···N25 | 1.00 | 2.46 | 3.353 (3) | 149 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1, −y+2, −z+1; (iii) −x+3/2, y−1/2, −z+1/2; (iv) −x+1, −y+1, −z; (v) x+1, y, z. |
Acknowledgements
We thank the Vietnam National University, Hanoi (grant No. QG.11.09) for the financial support of this work.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Supramolecular chemistry of azacrown ethers draws a great attention of researchers during the last decades (Hiraoka, 1982; Pedersen, 1988; Gokel & Murillo, 1996; Bradshaw & Izatt, 1997). Recently, we have developed effective methods of synthesis of azacrown ethers containing piperidine (Levov et al., 2006, 2008; Anh et al., 2008, 2012a, 2012b), perhydropyrimidine (Hieu et al., 2011) and perhydrotriazine (Hieu et al., 2009; Khieu et al., 2011) subunits.
In an attempt to apply these for a synthesis of a macrocyclic ligand with an N-methylsubstituted perhydrotriazine moiety, we studied the multicomponent condensation of thiourea with 1,5-bis(2-formylphenoxy)-3-oxapentane and methylammonium acetate. The reaction has proceeded smoothly under mild conditions to give the expected azacrown moiety in a good yield (Figure 1).
Compound I crystallizes as a chloroform solvate, i. e., C20H23N3O3S.CHCl3, with two crystallographically independent units within the unit cell. These crystallographically independent units represent two different molecular I.CHCl3 associates distinguished by different interactions between I and CHCl3 counterparts. In one of the two associates, the chloroform molecule forms the two C53—H53···N25 (as a protonodonor) and Cl2···H26A—C26 (as a protonoacceptor) hydrogen bonds (Table 1, Figure 2a), whereas, in the other associate, the chloroform molecule is bound to the molecule I by the attractive Cl6···O37 (3.080 (3) Å) interaction (Figure 2b). The azacrown macrocycles of the different I.CHCl3 associates are structurally similar.
The aza-14-crown-3-ether ring adopts a bowl conformation. The configuration of the C7—O8—C9—C10 —O11—C12—C13—O14—C15 polyether chain is t–g(-)–t–t–g(+)–t (t = trans, 180°; g = gauche, ±60°). The dihedral angles between the planes of the benzene rings fused to the aza-14-crown-3-ether moiety are 60.69 (8) and 68.01 (5)° for two crystallographically independent molecules, respectively. The triazinanethione ring has a sofa conformation - the nitrogen atoms N22, N24, N48 and N50 have a trigonal-planar geometry (sums of the bond angles are 358.8, 360.0, 359.0 and 359.9°, respectively), while the nitrogen N25 and N51 atoms adopt a trigonal-pyramidal geometry (sums of the bond angles are 331.9 and 333.7°, respectively).
The molecule of I possesses two asymmetric centers at the C1 and C21 carbon atoms and represents a meso-form (an internal racemate).
In the crystal, the molecular I.CHCl3 associates are linked by the intermolecular N—H···S, N—H···O, C—H···Cl and C—H···S hydrogen bonds into a three-dimensional framework (Table 1).