Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103018262/jz1569sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103018262/jz1569LTsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103018262/jz1569RTsup3.hkl |
CCDC references: 224496; 224497
All manipulations were carried out under nitrogen using a double manifold vacuum line, Schlenkware and cannula techniques. Tetrahydrofuran (THF) and hexane were distilled over sodium/benzophenone and dichloromethane (CH2Cl2) was distilled? over CaH2. Triphenylborane, 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane), and KSCN (Aldrich) were used as received. The following locally developed method was used to synthesize [K(18-crown-6)(SCN)]. To 18-crown-6 (10 g, 37.8 mmol) and KSCN (7.35 g, 75.6 mmol) in a two-neck 100 ml round-bottomed flask under nitrogen was added freshly distilled THF (100 ml). The solution was stired under nitrogen overnight. The product was filtered via cannula methods into a second (dry) round-bottomed flask prior to the slow addition of dry hexane to induce crystallization of the product. IR (cm-1, KBr pellet): 2054 [s, ν(C≡ N)], 847 [m, ν(C—S)], 464 [w, δ(N≡C—S)]. To triphenylborane (1.5 g, 6.17 mmol) and [K(18-crown-6)(SCN)] (1.49 g, 4.11 mmol) in a two-neck 100 ml round-bottomed flask under nitrogen was added freshly distilled CH2Cl2 (100 ml). The solution was stired under nitrogen for 4 h prior to cannula filtration into a second round- bottom flask under nitrogen. Dry hexane was added slowly in order to crystallize the product, viz. [K(18-crown-6)(SCNBPh3)] (isolated yield 1.66 g, 67%). A 12 mg portion was redissolved in freshly distilled CH2Cl2 (2.5 ml), transferred into a 18 × 180 mm Schlenk tube and layered with hexane. X-ray quality crystals were obtained after 8 d. IR (cm-1, KBr pellet): 2160 [s, ν(C≡N)], 840 [m, ν(C—S)], 470 [w, δ(N≡C—S)]; 1H NMR (499.98 MHz, CDCl3, p.p.m.): δ 7–7.4 (m, 15H, Ar—H), 3.47 (s, 12H, crown-CH2); 13C NMR (499.98 MHz, CDCl3, p.p.m.): δ 69.92 (CH2, 18-crown-6), 123.61 (p-C, BPh3), 125.35 (α-C, BPh3), 126.25 (m-C, BPh3), 126.97 (m-C, BPh3), 131.35 (o-C, BPh3), 133.41 (o-C, BPh3), 156.03 (C, NCS). AM1 geometry optimization calculations on SCN- and [SCNBPh3]- were carried out with the default singlet state parameters in HYPERCHEM 6.03.
A difference Fourier calculation after refinement of all non-H atoms anisotropically located most of the H atoms. However, all H atoms were refined using the standard riding model of SHELXL97 (Sheldrick, 1997). In the room-temperature structure of (I), rigid bond restraints (SHELXL97 DELU command) were used for atoms C26–C31, N1, C13, and S1, since large deviations (greater than 10 s.u.) were observed for the components of the anisotropic displacement parameters in the direction of the bonds involving these atoms. The absolute configuration of the crystal studied was determined from the Flack (1983) parameter, with 2428 Friedel pairs for the room- temperature structure and 3844 Friedel pairs for the low-temperature structure. Although we did not collect data from more than one crystal specimen, the bulk material is racemic, since the reactants are not chiral.
The thiocyanate ion is a well known ambidentate ligand that can coordinate to metal ions through the N atom (Sudbrake & Vahrenkamp, 2001) or the S atom (Uttecht & Preetz, 2001; Nelson et al., 1982). This property also favors the formation of dimeric and polymeric structures (Rudolph & Hartl, 1997; Zhang et al., 1997) in which the SCN- ion bridges identical or inequivalent metal ions to give homo- (M—S—C≡N—M) and heterobimetallic (M—S—C≡N—M') systems (Labahn et al., 1999; Harrowfield et al., 1996). Since N is a harder ligand donor than S (Pearson's classification of hard and soft bases), it is reasonable to assume that a soft metal ion, e.g. a 5 d or sixth-row main-group metal in a low oxidation state, would favor coordination to thiocyanate via the S atom (Drew et al., 1978). In contrast, hard metal ions would be expected to prefer coordination to the harder N donor and thus favor the formation of N-bound isothiocyanate complexes (Pohl et al., 1987). While these assumptions appear to be correct for many complexes, metal ions with an intermediate hard/soft character are clearly faced with two options as far as coordination to SCN- is concerned, with both N– and S-coordination to the same metal ion being found in several interesting cases (Nelson et al., 1982; Zhu et al., 2001). The fundamental question, therefore, is whether it is possible to control the manner in which thiocyanate binds to metal ions that are moderately soft.
We have recently begun an investigation of the structures and coordination chemistry of thiocyanate complexes of five- and six-coordinate FeIII and CoIII porphyrins in an effort to understand the factors that govern linkage isomerism and linear versus bent coordination of the SCN- ion in these systems (Pearson, 2002). During the course of this work, we realised that one way to control the delivery of the SCN- ion to the metal binding site is to tie up one of the donor atoms using the guiding principles of hard/soft acid/base (HSAB) theory, namely that the N atom of the SCN- ion is hard and may therefore be captured by a hard Lewis acid prior to delivery to the target metal ion (CoIII in the case of our work on porphyrins). In this paper, we show that triphenylborane (BPh3) is an easily handled Lewis acid that is well suited (if sterically bulky) to a role as an N-atom blocking group for the SCN- ion.
Selected structural parameters for (I) at 100 (1) and 293 (2) K are given in Tables 1 and 2, respectively. The following discussion pertains to the low-temperature data unless otherwise indicated. The ambidenticity of the SCN- ion is confirmed in Fig. 1(a), which clearly shows that the anion is axially coordinated to the K+ ion within the crown through its S atom and to the B atom of BPh3 through its N atom. The S1—K1 axial coordination interaction is characterized by a relatively long bond of 3.2617 (17) Å. However, since this is some 1.3 Å shorter than the sum of the van der Waals radii of the two bonded elements (4.55 Å), it is clearly a formal coordination interaction. The S1—K1 distance observed for (I) compares favorably with that reported for the YbIII derivative catena[bis(µ2-thiocyanato-N,S)-(18-crown-6)-potassium-bis(η5 -pentamethylcyclopentadienyl)ytterbium(III)] [3.226 (2) Å; Labahn et al., 1999]. The N1—B1 bond length, on the other hand, is 1.567 (3) Å and this is evidently a more regular dative covalent bond, particularly if we consider the mean B—C bond distance, which is 1.636 (5) Å. The K—O coordination distances average to 2.803 (38) Å; the large s.u. of the mean arises from the broad range [2.7666 (15)–2.8651 (15) Å; Table 1). The average cis-O—K—O and trans-O—K—O bond angles are 60.1 (6) and 167.9 (9)°, respectively. The marked deviation of the latter angle from 180° reflects the sizeable out-of-plane displacement of the K+ ion towards the axial S atom (see below).
The 18-crown-6 macrocycle has a conformation not unlike the teeth of a cylindrical saw, with the ring atoms alternately displaced above and below the mean plane of the [K(18-crown-6)]+ ion (Fig. 1 b). The maximum and minimum perpendicular atomic displacements from the mean plane of the macrocycle and K+ ion are -0.3810 (19) (C8) and 0.1352 (13) Å (O1), respectively. The K+ ion is displaced towards the axial S atom by 0.2829 (6) Å and the average value of the absolute perpendicular atomic displacements from the 19-atom mean plane is a substantial 0.257 (63) Å.
Coordination of the S atom of [SCNBPh3]- to the K+ ion of [K(18-crown-6)]+ is characterized by an unexpectedly narrow K1—S1—C13 angle of 94.98 (7)°. (The K—S—C angles in two other potassium thiocyanate derivatives are ~120°; Labahn et al., 1999; Habata et al., 2000.) Furthermore, the axial K1—S1 bond is substantially tilted from the normal to the mean plane of the metallated crown ether. This tilt is clearly evident from the O—K—S angles given in Table 1, which span a broad range from 78.98 (3) (for O3—K1—S1) to 111.48 (3)° (for O6—K1—S1), and from the view of (I) shown in Fig. 1(a). The origin of this marked structural distortion can be traced to the unexpected coordination of an aryl ring C atom to the potassium ion (trans to S1) from a neighboring molecule in the unit cell. The K1—C28iii distance [symmetry code: (iii) -x, y + 1/2, -z + 1/2] is 3.099 (3) Å and is therefore considerably shorter than the K1—S1 bond, even though the K+ ion is displaced towards the S atom. Moreover, since the K1—C29iii distance is 3.310 (3) Å, the K+ ion effectively shows asymmetric η2-type coordination to a C═C bond of the neighboring aryl ring. Organometallic complexes of potassium metal or K+ that exhibit both η1– and η2-coordination are well known (Kuhl et al., 1999; Chitsaz & Neumuller, 2001; Ganesan et al., 2002); the K—C distances are typically in the range 2.9–3.5 Å. Inspection of the Cambridge Structural Database (CSD; Allen, 2002) reveals that potassium readily forms organometallic complexes with coordination numbers as high as η8 to a single ligand in the case of bicyclic aromatic species (Cloke et al., 2000) or the cyclooctatetraenyl anion (Xia et al., 1991).
The trans-S1—K1—C28iii bond angle [159.10 (4)°] deviates significantly from 180° because of the close proximity of the crown ether to which atoms C28 and C29 are bound (Fig. 2). Steric repulsion between the neighboring crown ethers evidently requires that the K1—S1 bond and [SCNBPh3]- ion tilt away from the vector perpendicular to the mean plane of the cation in order to minimize unfavorable cation–cation and cation–anion non-bonded contacts. A useful descriptor of the lateral axial ligand displacement is the dihedral angle between the mean plane of the metallated crown ether and the triad K1—S1—C13, which is 71.75 (5)°. Interestingly, the 13C NMR spectrum of (I) showed two distinct ortho- and meta-carbon signals for the BPh3 phenyl groups, strongly suggesting that the K1—C28/C29 η2-coordination interaction observed in the solid state is also maintained in solution.
Inspection of the bond distances for (I) listed in Table 1 confirms that the thiocyanate ion has a Lewis structure that is fully consistent with a single bond between the S and C atoms and a C≡N triple bond. Furthermore, the S1—C13—N1—B1 tetrad is essentially linear, with the two bond angles subtended at atoms C13 and N1 falling within 5° of 180°. The assigned resonance form for the SCN- ion in this system is confirmed by the IR stretching frequencies for (I) (2160 cm-1 for the C≡N bond and 840 cm-1 for the C—S bond), which are typical values expected for such bonds (Nakamoto, 1986). Interestingly, the C≡N bond stretching frequency is shifted by 106 cm-1 to a higher wavenumber relative to [K(16-crown-6)(SCN)] upon coordination to BPh3. This shift reflects σ-electron donation from the N atom to a Lewis acid that is incapable of π-backbonding with the unsaturated ligand. Ultimately, an increase in polarity of the C≡N bond upon formation of the N—B bond results in the observed increase in the vibrational frequency. The key question is by how much does the electronic structure of the SCN- ion change with the addition of BPh3. Before we answer this question with AM1 (Dewar et al., 1985) calculations, it is noteworthy that the opposite appears to be true for the C—S bond, since the formation of complex (I) results in a small (7 cm-1) shift to lower frequency for the ν(CS) mode.
AM1 is parameterized for all of the elements present in (I) except K. Since our main objective in this work was to capture the N atom of the SCN- ion by coordination to boron, we have elected to focus on what effect B—N bond formation has on the electronic structure of the thiocyanate ion. The in vacuo AM1-calculated Mulliken charge distribution for [SCNBPh3]- is shown in Fig. 3(a), and that for the SCN- ion is given in Fig. 3(b). As implied by the change in the experimental vibrational frequency of the C≡N bond, the calculated charge distribution for the [SCNBPh3]- ion is consistent with marked polarization of the electron density by the B atom. Specifically, the partial negative charge on the N atom drops to 67% of its value in the free SCN- ion upon coordination to B. The fractional charge on the S atom decreases to ~54° of its value in SCN-. However, both of these changes are dwarfed by the drop in the partial negative charge for the central C atom from -0.161 e to -0.028 e (i.e. to 17° of its value in the free SCN- ion). More important is the fact that the S—C and C≡N bonds become more polar when the SCN- ion binds to BPh3. For example, the partial charge difference increases from 0.161 e to 0.188 e in going from SCN- to [SCNBPh3]- for the C≡N bond. In principle, stronger electrostatic attraction between the bonded atoms should increase the vibrational frequencies for the bonds constituting the SCN- ion.
It transpires that some useful information can be gleaned from the in vacuo AM1-calculated structures of the SCN- and [SCNBPh3]- ions. First, the calculated S—C (1.53 Å), C—N (1.18 Å), and N—B (1.53 Å) bond lengths of [SCNBPh3]- compare favorably with those determined experimentally for (I) (Table 1), even though the [K(18-crown-6)]+ ion was not included in the calculations. Secondly, the calculated S—C and C—N bond distances for the free SCN- ion (1.57 and 1.18 Å, respectively) reveal that coordination to BPh3 slightly increases the bond order, particularly of the C—S bond. The calculated vibrational frequencies for [SCNBPh3]- are thus higher [ν(C≡N) = 2385 cm-1, ν(C—S) = 855 cm-1] than for SCN- [ν(C≡N) = 2372 cm-1, ν(C—S) = 801 cm-1]. The calculated frequency change for the C≡N bond is smaller than that observed experimentally, whereas that for the C—S bond is larger and in the opposite direction. We surmise that these discrepancies probably reflect omission of the [K(18-crown-6)]+ ion from the simulations (particularly the S—K+ coordination interaction) and the relatively low level of theory inherent in the AM1 model. [We are currently running density functional theory (DFT) simulations on the present SCN- system, as well as thiocyanate and isothiocyanate complexes of a range of metalloporphyrins, in order to further elucidate the electronic structures of the SCN- ion in these species.]
The unit cell of (I) comprises four molecules (Fig. 4). As noted above, the somewhat unexpected coordination interaction between each K+ ion and the C═C bond of a neighboring BPh3 moiety leads to the formation of a helical polymer with an axis running parallel to the b axis of the unit cell, i.e. parallel to the vector joining adjacent potassium ions in the lattice. The coordination polymer may be formulated very simply by designation of its repeat unit, viz. {[K(18-crown-6)][SCNBPh3]}n. The significance of the chiral space group becomes more apparent upon inspection of the supramolecular structure of (I). Specifically, the polymer backbone, which includes the K+ ions and the ligand donor atoms S and C, is seen to spiral in a cork-screw fashion from left to right in a counterclockwise direction. Although we did not experimentally determine the absolute configuration of the crystal specimen used for the X-ray diffraction study, the left-handed helicity of the polymer chain is correct according to the Flack absolute structure parameter (Flack, 1983). (The bulk material is, of course, racemic.) Finally, it is noteworthy that other coordination polymers with bridging thiocyanate ions also crystallize in the chiral space group P212121 (Hehl & Thiele, 2000). A second, somewhat earlier, example is the copper(I) coordination polymer catena[(µ2-thiocyanato)-bis(quinoline)-copper(I)] (Healy et al., 1984).
Data collection: CrysAlis CCD (Oxford Diffraction, 2003) for LT; CAD-4 Software (Enraf–Nonius, ) for RT. Cell refinement: CrysAlis RED, (Oxford Diffraction, 2003) for LT; CAD-4 Software for RT. Data reduction: CrysAlis RED for LT; PROFIT (Streltsov & Zavodnik, 1989) for RT. For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: WinGX WinGX (Farrugia, 1999) and ORTEP-3 for Windows (Farrugia, 1997) for LT; WinGX (Farrugia, 1999) and ORTEP-3 for Windows (Farrugia, 1997) for RT. For both compounds, software used to prepare material for publication: WinGX.
[K(C19H15BNS)(C12H24O6)] | F(000) = 1280 |
Mr = 603.6 | Dx = 1.299 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 285 reflections |
a = 11.034 (4) Å | θ = 4.2–31.7° |
b = 11.582 (9) Å | µ = 0.28 mm−1 |
c = 24.149 (7) Å | T = 100 K |
V = 3086 (3) Å3 | Rhomb, colorless |
Z = 4 | 0.53 × 0.33 × 0.22 mm |
Oxford Diffraction Xcalibur2 CCD diffractometer | 8301 reflections with I > 2σ(I) |
ω–2θ scans | Rint = 0.048 |
Absorption correction: numerical CrysAlis RED, Oxford Diffraction Ltd., Version 1.170.32 (release 06/06/2003 CrysAlis170 VC++). Analytical numeric absorption correction using a multifaceted crystal model. | θmax = 31.7°, θmin = 4.2° |
Tmin = 0.810, Tmax = 0.900 | h = −16→15 |
28274 measured reflections | k = −11→17 |
9621 independent reflections | l = −35→35 |
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0276P)2 + 1.8032P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.047 | (Δ/σ)max = 0.001 |
wR(F2) = 0.095 | Δρmax = 0.48 e Å−3 |
S = 1.08 | Δρmin = −0.40 e Å−3 |
9621 reflections | Absolute structure: Flack (1983) |
370 parameters | Absolute structure parameter: 0.08 (3) |
0 restraints |
[K(C19H15BNS)(C12H24O6)] | V = 3086 (3) Å3 |
Mr = 603.6 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 11.034 (4) Å | µ = 0.28 mm−1 |
b = 11.582 (9) Å | T = 100 K |
c = 24.149 (7) Å | 0.53 × 0.33 × 0.22 mm |
Oxford Diffraction Xcalibur2 CCD diffractometer | 9621 independent reflections |
Absorption correction: numerical CrysAlis RED, Oxford Diffraction Ltd., Version 1.170.32 (release 06/06/2003 CrysAlis170 VC++). Analytical numeric absorption correction using a multifaceted crystal model. | 8301 reflections with I > 2σ(I) |
Tmin = 0.810, Tmax = 0.900 | Rint = 0.048 |
28274 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.095 | Δρmax = 0.48 e Å−3 |
S = 1.08 | Δρmin = −0.40 e Å−3 |
9621 reflections | Absolute structure: Flack (1983) |
370 parameters | Absolute structure parameter: 0.08 (3) |
0 restraints |
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. LEAST-SQUARES PLANES: Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 1.6613 (0.0023) x + 10.4526 (0.0081) y - 9.7436 (0.0086) z = 1.6306 (0.0023) * 0.2829 (0.0006) K1 * 0.1352 (0.0013) O1 * -0.2659 (0.0013) O2 * 0.1837 (0.0013) O3 * -0.1777 (0.0013) O4 * 0.2050 (0.0013) O5 * -0.1635 (0.0013) O6 * -0.3279 (0.0018) C1 * 0.2546 (0.0018) C2 * 0.2764 (0.0017) C3 * -0.2572 (0.0017) C4 * -0.2795 (0.0018) C5 * 0.3077 (0.0018) C6 * 0.2049 (0.0018) C7 * -0.3810 (0.0019) C8 * -0.3075 (0.0018) C9 * 0.2797 (0.0018) C10 * 0.3140 (0.0018) C11 * -0.2839 (0.0017) C12 3.3613 (0.0027) S1 Rms deviation of fitted atoms = 0.2646 4.0287 (0.0089) x + 4.4418 (0.0090) y - 20.4855 (0.0188) z = 4.7597 (0.0100) Angle to [K(18-crown-6)]+ plane (with approximate e.s.d.) = 41.98 (0.07) * 0.0095 (0.0013) C14 * -0.0042 (0.0013) C15 * -0.0043 (0.0014) C16 * 0.0076 (0.0014) C17 * -0.0020 (0.0015) C18 * -0.0065 (0.0014) C19 Rms deviation of fitted atoms = 0.0062 5.4502 (0.0093) x + 6.3990 (0.0093) y + 16.2134 (0.0192) z = 9.8703 (0.0114) Angle to [K(18-crown-6)]+ plane (with approximate e.s.d.) = 72.41 (0.06) * 0.0246 (0.0013) C20 * -0.0068 (0.0014) C21 * -0.0136 (0.0015) C22 * 0.0164 (0.0015) C23 * 0.0021 (0.0015) C24 * -0.0226 (0.0014) C25 Rms deviation of fitted atoms = 0.0165 -2.0257 (0.0080) x + 11.3250 (0.0089) y - 2.4297 (0.0180) z = 3.0150 (0.0112) Angle to [K(18-crown-6)]+ plane (with approximate e.s.d.) = 26.43 (0.06) * -0.0065 (0.0013) C26 * 0.0080 (0.0013) C27 * -0.0018 (0.0012) C28 * -0.0058 (0.0013) C29 * 0.0070 (0.0013) C30 * -0.0009 (0.0013) C31 Rms deviation of fitted atoms = 0.0057 5.2739 (0.0123) x + 6.5682 (0.0065) y + 16.1985 (0.0174) z = 9.8557 (0.0090) Angle to [K(18-crown-6)]+ plane (with approximate e.s.d.) = 71.75 (0.05) * 0.0000 (0.0000) K1 * 0.0000 (0.0000) S1 * 0.0000 (0.0000) C13 Rms deviation of fitted atoms = 0.0000 |
x | y | z | Uiso*/Ueq | ||
C20 | 1.06812 (16) | 0.56678 (15) | 0.02755 (7) | 0.0176 (3) | |
C21 | 0.97882 (18) | 0.65149 (17) | 0.02219 (8) | 0.0232 (4) | |
H21 | 0.9098 | 0.6482 | 0.0456 | 0.028* | |
C22 | 0.9875 (2) | 0.74075 (18) | −0.01637 (9) | 0.0297 (4) | |
H22 | 0.9247 | 0.7967 | −0.0189 | 0.036* | |
C23 | 1.0877 (2) | 0.74827 (18) | −0.05119 (9) | 0.0297 (4) | |
H23 | 1.0957 | 0.8105 | −0.0766 | 0.036* | |
C24 | 1.1753 (2) | 0.66349 (19) | −0.04806 (9) | 0.0278 (4) | |
H24 | 1.2438 | 0.6667 | −0.0719 | 0.033* | |
C25 | 1.16438 (18) | 0.57319 (17) | −0.01025 (8) | 0.0220 (4) | |
H25 | 1.224 | 0.514 | −0.0101 | 0.026* | |
C26 | 1.17329 (16) | 0.50195 (15) | 0.12321 (7) | 0.0173 (3) | |
C27 | 1.14956 (17) | 0.51109 (15) | 0.17967 (8) | 0.0199 (3) | |
H27 | 1.0687 | 0.5008 | 0.1922 | 0.024* | |
C28 | 1.23980 (18) | 0.53471 (15) | 0.21853 (7) | 0.0229 (4) | |
H28 | 1.2204 | 0.5391 | 0.2568 | 0.027* | |
C29 | 1.35707 (17) | 0.55158 (15) | 0.20104 (8) | 0.0218 (4) | |
H29 | 1.4187 | 0.5672 | 0.2274 | 0.026* | |
C30 | 1.38567 (17) | 0.54605 (16) | 0.14618 (9) | 0.0239 (4) | |
H30 | 1.4666 | 0.5592 | 0.1343 | 0.029* | |
C31 | 1.29577 (16) | 0.52105 (16) | 0.10783 (8) | 0.0212 (4) | |
H31 | 1.3171 | 0.5165 | 0.0698 | 0.025* | |
C1 | 0.78360 (17) | 0.11215 (17) | 0.12022 (8) | 0.0227 (4) | |
H1A | 0.7656 | 0.0363 | 0.1373 | 0.027* | |
H1B | 0.8245 | 0.0985 | 0.0843 | 0.027* | |
C2 | 0.66812 (18) | 0.17775 (18) | 0.11113 (8) | 0.0236 (4) | |
H2A | 0.6866 | 0.2561 | 0.097 | 0.028* | |
H2B | 0.6175 | 0.1375 | 0.0833 | 0.028* | |
C3 | 0.49397 (17) | 0.24862 (16) | 0.15521 (8) | 0.0227 (4) | |
H3A | 0.4411 | 0.2081 | 0.1284 | 0.027* | |
H3B | 0.5118 | 0.3265 | 0.1404 | 0.027* | |
C4 | 0.43034 (17) | 0.25881 (16) | 0.21006 (9) | 0.0224 (4) | |
H4A | 0.3515 | 0.2983 | 0.2052 | 0.027* | |
H4B | 0.415 | 0.181 | 0.2256 | 0.027* | |
C5 | 0.45012 (17) | 0.33699 (17) | 0.29959 (8) | 0.0234 (4) | |
H5A | 0.4402 | 0.2608 | 0.3176 | 0.028* | |
H5B | 0.369 | 0.3726 | 0.2955 | 0.028* | |
C6 | 0.52990 (17) | 0.41288 (16) | 0.33434 (9) | 0.0240 (4) | |
H6A | 0.5427 | 0.4879 | 0.3156 | 0.029* | |
H6B | 0.4912 | 0.4276 | 0.3706 | 0.029* | |
C7 | 0.7190 (2) | 0.41564 (17) | 0.38009 (9) | 0.0259 (4) | |
H7A | 0.677 | 0.4244 | 0.4161 | 0.031* | |
H7B | 0.7378 | 0.4936 | 0.3656 | 0.031* | |
C8 | 0.83313 (19) | 0.34850 (18) | 0.38765 (8) | 0.0254 (4) | |
H8A | 0.8835 | 0.3848 | 0.4168 | 0.03* | |
H8B | 0.8138 | 0.2687 | 0.3994 | 0.03* | |
C9 | 1.00926 (17) | 0.28457 (17) | 0.34157 (8) | 0.0234 (3) | |
H9A | 0.9928 | 0.2053 | 0.355 | 0.028* | |
H9B | 1.0623 | 0.3234 | 0.3689 | 0.028* | |
C10 | 1.07167 (17) | 0.27949 (18) | 0.28649 (8) | 0.0237 (4) | |
H10A | 1.0834 | 0.3585 | 0.2718 | 0.028* | |
H10B | 1.1522 | 0.2429 | 0.2906 | 0.028* | |
C11 | 1.05431 (17) | 0.20156 (18) | 0.19641 (8) | 0.0231 (4) | |
H11A | 1.1361 | 0.1676 | 0.2005 | 0.028* | |
H11B | 1.0626 | 0.278 | 0.1785 | 0.028* | |
C12 | 0.97639 (16) | 0.12424 (16) | 0.16155 (9) | 0.0212 (3) | |
H12A | 1.014 | 0.113 | 0.1247 | 0.025* | |
H12B | 0.9678 | 0.0478 | 0.1795 | 0.025* | |
C13 | 0.85403 (16) | 0.49274 (16) | 0.13058 (8) | 0.0200 (3) | |
C14 | 1.08267 (16) | 0.33891 (15) | 0.05359 (7) | 0.0179 (3) | |
C15 | 1.18601 (17) | 0.27076 (16) | 0.05981 (9) | 0.0231 (4) | |
H15 | 1.253 | 0.3007 | 0.0799 | 0.028* | |
C16 | 1.1940 (2) | 0.15982 (18) | 0.03734 (9) | 0.0271 (4) | |
H16 | 1.2659 | 0.1159 | 0.0424 | 0.033* | |
C17 | 1.0984 (2) | 0.11353 (17) | 0.00792 (9) | 0.0301 (5) | |
H17 | 1.1043 | 0.0386 | −0.0079 | 0.036* | |
C18 | 0.9936 (2) | 0.17833 (18) | 0.00183 (9) | 0.0299 (4) | |
H18 | 0.9266 | 0.1474 | −0.0179 | 0.036* | |
C19 | 0.98631 (18) | 0.28849 (18) | 0.02450 (8) | 0.0244 (4) | |
H19 | 0.9134 | 0.3311 | 0.0201 | 0.029* | |
B1 | 1.06976 (18) | 0.47045 (17) | 0.07735 (8) | 0.0168 (3) | |
K1 | 0.75560 (3) | 0.29088 (3) | 0.244481 (15) | 0.01968 (8) | |
N1 | 0.94420 (14) | 0.47798 (14) | 0.10741 (7) | 0.0203 (3) | |
O1 | 0.86023 (11) | 0.17730 (11) | 0.15564 (6) | 0.0194 (3) | |
O2 | 0.60422 (11) | 0.18583 (11) | 0.16230 (6) | 0.0193 (3) | |
O3 | 0.50500 (11) | 0.32328 (11) | 0.24670 (6) | 0.0205 (2) | |
O4 | 0.64292 (12) | 0.35562 (11) | 0.34200 (6) | 0.0218 (3) | |
O5 | 0.89824 (12) | 0.34645 (11) | 0.33642 (6) | 0.0213 (3) | |
O6 | 0.99893 (11) | 0.21402 (11) | 0.24935 (6) | 0.0212 (2) | |
S1 | 0.72694 (4) | 0.51422 (4) | 0.16325 (2) | 0.02857 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C20 | 0.0191 (8) | 0.0189 (8) | 0.0148 (8) | 0.0006 (6) | −0.0027 (6) | −0.0014 (6) |
C21 | 0.0249 (9) | 0.0255 (9) | 0.0194 (9) | 0.0058 (7) | −0.0013 (7) | 0.0006 (7) |
C22 | 0.0391 (11) | 0.0255 (10) | 0.0245 (10) | 0.0086 (8) | −0.0072 (9) | 0.0027 (8) |
C23 | 0.0453 (12) | 0.0258 (9) | 0.0179 (10) | −0.0030 (9) | −0.0048 (9) | 0.0047 (7) |
C24 | 0.0291 (10) | 0.0327 (10) | 0.0217 (10) | −0.0044 (8) | 0.0011 (8) | 0.0037 (8) |
C25 | 0.0208 (8) | 0.0257 (9) | 0.0196 (9) | 0.0013 (7) | 0.0004 (7) | 0.0004 (7) |
C26 | 0.0183 (7) | 0.0159 (8) | 0.0177 (8) | 0.0030 (6) | −0.0010 (6) | 0.0012 (6) |
C27 | 0.0214 (8) | 0.0182 (8) | 0.0203 (9) | 0.0015 (7) | 0.0016 (6) | −0.0005 (7) |
C28 | 0.0316 (9) | 0.0206 (8) | 0.0164 (8) | 0.0005 (8) | −0.0018 (7) | −0.0009 (6) |
C29 | 0.0236 (9) | 0.0152 (8) | 0.0266 (10) | 0.0020 (6) | −0.0067 (7) | 0.0018 (7) |
C30 | 0.0179 (8) | 0.0215 (9) | 0.0323 (11) | −0.0028 (7) | −0.0030 (7) | 0.0040 (7) |
C31 | 0.0194 (8) | 0.0214 (8) | 0.0227 (9) | 0.0006 (7) | −0.0003 (6) | 0.0016 (7) |
C1 | 0.0229 (9) | 0.0268 (9) | 0.0184 (9) | 0.0000 (7) | 0.0014 (7) | −0.0046 (7) |
C2 | 0.0247 (9) | 0.0298 (10) | 0.0163 (9) | 0.0015 (7) | −0.0011 (7) | −0.0004 (7) |
C3 | 0.0199 (8) | 0.0216 (8) | 0.0267 (10) | 0.0028 (7) | −0.0054 (7) | 0.0001 (7) |
C4 | 0.0159 (8) | 0.0225 (8) | 0.0287 (10) | 0.0006 (7) | −0.0014 (7) | −0.0019 (7) |
C5 | 0.0205 (8) | 0.0242 (9) | 0.0255 (10) | 0.0020 (7) | 0.0067 (7) | 0.0018 (7) |
C6 | 0.0256 (9) | 0.0210 (8) | 0.0255 (10) | 0.0041 (7) | 0.0063 (8) | −0.0002 (7) |
C7 | 0.0326 (10) | 0.0240 (9) | 0.0210 (9) | −0.0033 (8) | 0.0031 (8) | −0.0062 (7) |
C8 | 0.0295 (10) | 0.0284 (10) | 0.0182 (9) | −0.0041 (8) | −0.0006 (7) | 0.0003 (7) |
C9 | 0.0226 (8) | 0.0241 (8) | 0.0234 (9) | −0.0029 (7) | −0.0063 (7) | 0.0008 (7) |
C10 | 0.0184 (8) | 0.0259 (9) | 0.0269 (10) | −0.0044 (7) | −0.0051 (7) | 0.0006 (8) |
C11 | 0.0175 (8) | 0.0270 (9) | 0.0246 (9) | −0.0013 (7) | 0.0043 (7) | −0.0005 (8) |
C12 | 0.0166 (8) | 0.0219 (8) | 0.0250 (10) | 0.0013 (6) | 0.0053 (7) | −0.0018 (7) |
C13 | 0.0184 (8) | 0.0201 (8) | 0.0216 (9) | −0.0006 (7) | −0.0014 (6) | 0.0029 (7) |
C14 | 0.0198 (8) | 0.0193 (8) | 0.0147 (8) | −0.0011 (6) | 0.0008 (6) | 0.0025 (6) |
C15 | 0.0207 (8) | 0.0230 (9) | 0.0254 (10) | −0.0013 (7) | 0.0037 (7) | 0.0021 (7) |
C16 | 0.0312 (10) | 0.0224 (9) | 0.0277 (11) | 0.0025 (8) | 0.0104 (8) | 0.0050 (8) |
C17 | 0.0493 (13) | 0.0190 (9) | 0.0220 (10) | −0.0041 (8) | 0.0099 (9) | 0.0001 (7) |
C18 | 0.0397 (12) | 0.0287 (10) | 0.0212 (10) | −0.0106 (9) | −0.0012 (9) | −0.0013 (7) |
C19 | 0.0244 (9) | 0.0273 (9) | 0.0214 (9) | −0.0030 (8) | −0.0044 (7) | 0.0012 (8) |
B1 | 0.0154 (8) | 0.0198 (9) | 0.0153 (9) | 0.0001 (7) | 0.0001 (7) | 0.0017 (7) |
K1 | 0.01825 (16) | 0.02143 (15) | 0.01936 (17) | 0.00152 (14) | −0.00073 (14) | −0.00215 (13) |
N1 | 0.0164 (6) | 0.0242 (7) | 0.0203 (8) | 0.0006 (6) | −0.0015 (5) | 0.0013 (6) |
O1 | 0.0177 (6) | 0.0205 (6) | 0.0200 (7) | 0.0017 (5) | −0.0007 (5) | −0.0017 (5) |
O2 | 0.0171 (5) | 0.0223 (6) | 0.0186 (6) | 0.0037 (4) | −0.0016 (5) | 0.0003 (5) |
O3 | 0.0156 (5) | 0.0246 (6) | 0.0213 (6) | −0.0012 (4) | 0.0023 (5) | −0.0014 (5) |
O4 | 0.0220 (6) | 0.0204 (6) | 0.0231 (7) | 0.0007 (5) | 0.0006 (5) | −0.0030 (5) |
O5 | 0.0227 (6) | 0.0235 (6) | 0.0176 (7) | −0.0018 (5) | −0.0021 (5) | 0.0006 (5) |
O6 | 0.0171 (5) | 0.0266 (6) | 0.0201 (6) | −0.0041 (5) | −0.0001 (5) | −0.0011 (6) |
S1 | 0.0184 (2) | 0.0295 (2) | 0.0378 (3) | 0.00466 (17) | 0.00867 (19) | 0.0070 (2) |
C20—C21 | 1.397 (3) | C6—H6B | 0.99 |
C20—C25 | 1.403 (3) | C7—O4 | 1.426 (2) |
C20—B1 | 1.641 (3) | C7—C8 | 1.492 (3) |
C21—C22 | 1.395 (3) | C7—H7A | 0.99 |
C21—H21 | 0.95 | C7—H7B | 0.99 |
C22—C23 | 1.392 (3) | C8—O5 | 1.431 (2) |
C22—H22 | 0.95 | C8—H8A | 0.99 |
C23—C24 | 1.380 (3) | C8—H8B | 0.99 |
C23—H23 | 0.95 | C9—O5 | 1.425 (2) |
C24—C25 | 1.394 (3) | C9—C10 | 1.499 (3) |
C24—H24 | 0.95 | C9—H9A | 0.99 |
C25—H25 | 0.95 | C9—H9B | 0.99 |
C26—C27 | 1.392 (3) | C10—O6 | 1.423 (2) |
C26—C31 | 1.419 (2) | C10—H10A | 0.99 |
C26—B1 | 1.632 (3) | C10—H10B | 0.99 |
C27—C28 | 1.395 (3) | C11—O6 | 1.424 (2) |
C27—H27 | 0.95 | C11—C12 | 1.500 (3) |
C28—C29 | 1.375 (3) | C11—H11A | 0.99 |
C28—K1i | 3.099 (3) | C11—H11B | 0.99 |
C28—H28 | 0.95 | C12—O1 | 1.429 (2) |
C29—C30 | 1.364 (3) | C12—H12A | 0.99 |
C29—K1i | 3.310 (3) | C12—H12B | 0.99 |
C29—H29 | 0.95 | C13—N1 | 1.154 (2) |
C30—C31 | 1.388 (3) | C13—S1 | 1.6282 (19) |
C30—H30 | 0.95 | C14—C15 | 1.395 (3) |
C31—H31 | 0.95 | C14—C19 | 1.402 (3) |
C1—O1 | 1.420 (2) | C14—B1 | 1.634 (3) |
C1—C2 | 1.500 (3) | C15—C16 | 1.398 (3) |
C1—H1A | 0.99 | C15—H15 | 0.95 |
C1—H1B | 0.99 | C16—C17 | 1.380 (3) |
C2—O2 | 1.426 (2) | C16—H16 | 0.95 |
C2—H2A | 0.99 | C17—C18 | 1.386 (3) |
C2—H2B | 0.99 | C17—H17 | 0.95 |
C3—O2 | 1.428 (2) | C18—C19 | 1.391 (3) |
C3—C4 | 1.504 (3) | C18—H18 | 0.95 |
C3—H3A | 0.99 | C19—H19 | 0.95 |
C3—H3B | 0.99 | B1—N1 | 1.567 (3) |
C4—O3 | 1.421 (2) | K1—O4 | 2.7666 (15) |
C4—H4A | 0.99 | K1—O1 | 2.7687 (15) |
C4—H4B | 0.99 | K1—O3 | 2.7911 (16) |
C5—O3 | 1.423 (2) | K1—O5 | 2.7966 (15) |
C5—C6 | 1.500 (3) | K1—O6 | 2.8312 (16) |
C5—H5A | 0.99 | K1—O2 | 2.8651 (15) |
C5—H5B | 0.99 | K1—C28ii | 3.099 (3) |
C6—O4 | 1.424 (2) | K1—S1 | 3.2617 (17) |
C6—H6A | 0.99 | K1—C29ii | 3.310 (3) |
C21—C20—C25 | 115.91 (17) | C9—C10—H10A | 109.9 |
C21—C20—B1 | 123.61 (17) | O6—C10—H10B | 109.9 |
C25—C20—B1 | 120.31 (16) | C9—C10—H10B | 109.9 |
C22—C21—C20 | 122.28 (19) | H10A—C10—H10B | 108.3 |
C22—C21—H21 | 118.9 | O6—C11—C12 | 108.56 (15) |
C20—C21—H21 | 118.9 | O6—C11—H11A | 110 |
C23—C22—C21 | 120.28 (19) | C12—C11—H11A | 110 |
C23—C22—H22 | 119.9 | O6—C11—H11B | 110 |
C21—C22—H22 | 119.9 | C12—C11—H11B | 110 |
C24—C23—C22 | 118.62 (19) | H11A—C11—H11B | 108.4 |
C24—C23—H23 | 120.7 | O1—C12—C11 | 108.28 (15) |
C22—C23—H23 | 120.7 | O1—C12—H12A | 110 |
C23—C24—C25 | 120.6 (2) | C11—C12—H12A | 110 |
C23—C24—H24 | 119.7 | O1—C12—H12B | 110 |
C25—C24—H24 | 119.7 | C11—C12—H12B | 110 |
C24—C25—C20 | 122.13 (18) | H12A—C12—H12B | 108.4 |
C24—C25—H25 | 118.9 | N1—C13—S1 | 179.7 (2) |
C20—C25—H25 | 118.9 | C15—C14—C19 | 115.99 (18) |
C27—C26—C31 | 115.06 (17) | C15—C14—B1 | 124.12 (16) |
C27—C26—B1 | 123.35 (16) | C19—C14—B1 | 119.88 (16) |
C31—C26—B1 | 121.59 (16) | C14—C15—C16 | 122.01 (19) |
C26—C27—C28 | 122.63 (17) | C14—C15—H15 | 119 |
C26—C27—H27 | 118.7 | C16—C15—H15 | 119 |
C28—C27—H27 | 118.7 | C17—C16—C15 | 120.6 (2) |
C29—C28—C27 | 119.54 (17) | C17—C16—H16 | 119.7 |
C29—C28—K1i | 86.39 (11) | C15—C16—H16 | 119.7 |
C27—C28—K1i | 113.15 (12) | C16—C17—C18 | 118.80 (19) |
C29—C28—H28 | 120.2 | C16—C17—H17 | 120.6 |
C27—C28—H28 | 120.2 | C18—C17—H17 | 120.6 |
K1i—C28—H28 | 70.9 | C17—C18—C19 | 120.2 (2) |
C30—C29—C28 | 120.63 (18) | C17—C18—H18 | 119.9 |
C30—C29—K1i | 120.82 (13) | C19—C18—H18 | 119.9 |
C28—C29—K1i | 69.12 (11) | C18—C19—C14 | 122.37 (19) |
C30—C29—H29 | 119.7 | C18—C19—H19 | 118.8 |
C28—C29—H29 | 119.7 | C14—C19—H19 | 118.8 |
K1i—C29—H29 | 80.9 | N1—B1—C26 | 106.98 (14) |
C29—C30—C31 | 119.53 (18) | N1—B1—C14 | 106.96 (14) |
C29—C30—H30 | 120.2 | C26—B1—C14 | 112.67 (14) |
C31—C30—H30 | 120.2 | N1—B1—C20 | 106.98 (14) |
C30—C31—C26 | 122.60 (18) | C26—B1—C20 | 110.68 (15) |
C30—C31—H31 | 118.7 | C14—B1—C20 | 112.19 (15) |
C26—C31—H31 | 118.7 | O4—K1—O1 | 167.35 (4) |
O1—C1—C2 | 108.96 (15) | O4—K1—O3 | 60.13 (4) |
O1—C1—H1A | 109.9 | O1—K1—O3 | 119.46 (4) |
C2—C1—H1A | 109.9 | O4—K1—O5 | 60.97 (5) |
O1—C1—H1B | 109.9 | O1—K1—O5 | 119.33 (4) |
C2—C1—H1B | 109.9 | O3—K1—O5 | 120.76 (4) |
H1A—C1—H1B | 108.3 | O4—K1—O6 | 118.43 (4) |
O2—C2—C1 | 109.06 (15) | O1—K1—O6 | 59.16 (4) |
O2—C2—H2A | 109.9 | O3—K1—O6 | 168.84 (4) |
C1—C2—H2A | 109.9 | O5—K1—O6 | 60.37 (4) |
O2—C2—H2B | 109.9 | O4—K1—O2 | 116.27 (4) |
C1—C2—H2B | 109.9 | O1—K1—O2 | 60.31 (4) |
H2A—C2—H2B | 108.3 | O3—K1—O2 | 59.52 (4) |
O2—C3—C4 | 109.41 (15) | O5—K1—O2 | 167.36 (4) |
O2—C3—H3A | 109.8 | O6—K1—O2 | 116.63 (4) |
C4—C3—H3A | 109.8 | O4—K1—C28ii | 91.23 (5) |
O2—C3—H3B | 109.8 | O1—K1—C28ii | 76.21 (5) |
C4—C3—H3B | 109.8 | O3—K1—C28ii | 98.01 (5) |
H3A—C3—H3B | 108.2 | O5—K1—C28ii | 88.98 (5) |
O3—C4—C3 | 108.60 (15) | O6—K1—C28ii | 70.82 (5) |
O3—C4—H4A | 110 | O2—K1—C28ii | 78.62 (5) |
C3—C4—H4A | 110 | O4—K1—S1 | 104.68 (4) |
O3—C4—H4B | 110 | O1—K1—S1 | 87.20 (5) |
C3—C4—H4B | 110 | O3—K1—S1 | 78.98 (3) |
H4A—C4—H4B | 108.4 | O5—K1—S1 | 110.46 (4) |
O3—C5—C6 | 108.52 (15) | O6—K1—S1 | 111.48 (3) |
O3—C5—H5A | 110 | O2—K1—S1 | 82.16 (5) |
C6—C5—H5A | 110 | C28ii—K1—S1 | 159.10 (4) |
O3—C5—H5B | 110 | O4—K1—C29ii | 73.73 (5) |
C6—C5—H5B | 110 | O1—K1—C29ii | 93.83 (6) |
H5A—C5—H5B | 108.4 | O3—K1—C29ii | 74.51 (5) |
O4—C6—C5 | 108.28 (15) | O5—K1—C29ii | 95.08 (5) |
O4—C6—H6A | 110 | O6—K1—C29ii | 94.39 (5) |
C5—C6—H6A | 110 | O2—K1—C29ii | 72.59 (5) |
O4—C6—H6B | 110 | C28ii—K1—C29ii | 24.49 (5) |
C5—C6—H6B | 110 | S1—K1—C29ii | 150.06 (4) |
H6A—C6—H6B | 108.4 | C13—N1—B1 | 174.41 (18) |
O4—C7—C8 | 108.78 (16) | C1—O1—C12 | 111.46 (14) |
O4—C7—H7A | 109.9 | C1—O1—K1 | 118.10 (10) |
C8—C7—H7A | 109.9 | C12—O1—K1 | 120.08 (11) |
O4—C7—H7B | 109.9 | C2—O2—C3 | 110.54 (14) |
C8—C7—H7B | 109.9 | C2—O2—K1 | 109.87 (10) |
H7A—C7—H7B | 108.3 | C3—O2—K1 | 111.32 (11) |
O5—C8—C7 | 109.07 (16) | C4—O3—C5 | 111.78 (14) |
O5—C8—H8A | 109.9 | C4—O3—K1 | 119.46 (10) |
C7—C8—H8A | 109.9 | C5—O3—K1 | 117.00 (11) |
O5—C8—H8B | 109.9 | C6—O4—C7 | 111.84 (15) |
C7—C8—H8B | 109.9 | C6—O4—K1 | 114.14 (11) |
H8A—C8—H8B | 108.3 | C7—O4—K1 | 114.63 (11) |
O5—C9—C10 | 109.72 (15) | C9—O5—C8 | 111.39 (15) |
O5—C9—H9A | 109.7 | C9—O5—K1 | 115.94 (11) |
C10—C9—H9A | 109.7 | C8—O5—K1 | 114.06 (11) |
O5—C9—H9B | 109.7 | C10—O6—C11 | 112.21 (14) |
C10—C9—H9B | 109.7 | C10—O6—K1 | 113.18 (11) |
H9A—C9—H9B | 108.2 | C11—O6—K1 | 113.67 (10) |
O6—C10—C9 | 108.74 (15) | C13—S1—K1 | 94.98 (7) |
O6—C10—H10A | 109.9 | ||
C25—C20—C21—C22 | −3.3 (3) | S1—K1—O2—C3 | −56.52 (11) |
B1—C20—C21—C22 | 171.96 (18) | C29ii—K1—O2—C3 | 107.20 (12) |
C20—C21—C22—C23 | −0.2 (3) | C3—C4—O3—C5 | 179.71 (15) |
C21—C22—C23—C24 | 2.4 (3) | C3—C4—O3—K1 | −38.37 (18) |
C22—C23—C24—C25 | −0.9 (3) | C6—C5—O3—C4 | −175.91 (15) |
C23—C24—C25—C20 | −2.8 (3) | C6—C5—O3—K1 | 41.16 (18) |
C21—C20—C25—C24 | 4.8 (3) | O4—K1—O3—C4 | −150.45 (13) |
B1—C20—C25—C24 | −170.61 (18) | O1—K1—O3—C4 | 14.99 (13) |
C31—C26—C27—C28 | −1.4 (3) | O5—K1—O3—C4 | −157.26 (12) |
B1—C26—C27—C28 | 178.04 (16) | O6—K1—O3—C4 | −64.7 (3) |
C26—C27—C28—C29 | 1.0 (3) | O2—K1—O3—C4 | 8.04 (11) |
C26—C27—C28—K1i | 100.42 (18) | C28ii—K1—O3—C4 | −63.65 (13) |
C27—C28—C29—C30 | 0.4 (3) | S1—K1—O3—C4 | 95.37 (13) |
K1i—C28—C29—C30 | −114.30 (17) | C29ii—K1—O3—C4 | −70.59 (13) |
C27—C28—C29—K1i | 114.65 (17) | O4—K1—O3—C5 | −10.45 (11) |
C28—C29—C30—C31 | −1.2 (3) | O1—K1—O3—C5 | 154.99 (11) |
K1i—C29—C30—C31 | −83.8 (2) | O5—K1—O3—C5 | −17.27 (13) |
C29—C30—C31—C26 | 0.7 (3) | O6—K1—O3—C5 | 75.3 (3) |
C27—C26—C31—C30 | 0.5 (3) | O2—K1—O3—C5 | 148.04 (13) |
B1—C26—C31—C30 | −178.91 (17) | C28ii—K1—O3—C5 | 76.34 (12) |
O1—C1—C2—O2 | −65.64 (19) | S1—K1—O3—C5 | −124.63 (12) |
O2—C3—C4—O3 | 62.91 (19) | C29ii—K1—O3—C5 | 69.41 (12) |
O3—C5—C6—O4 | −63.08 (19) | C5—C6—O4—C7 | −172.99 (16) |
O4—C7—C8—O5 | 65.2 (2) | C5—C6—O4—K1 | 54.81 (17) |
O5—C9—C10—O6 | −64.7 (2) | C8—C7—O4—C6 | 177.83 (16) |
O6—C11—C12—O1 | 60.8 (2) | C8—C7—O4—K1 | −50.22 (18) |
C19—C14—C15—C16 | 1.4 (3) | O1—K1—O4—C6 | −115.6 (2) |
B1—C14—C15—C16 | −178.10 (17) | O3—K1—O4—C6 | −23.85 (11) |
C14—C15—C16—C17 | −0.1 (3) | O5—K1—O4—C6 | 149.46 (13) |
C15—C16—C17—C18 | −1.0 (3) | O6—K1—O4—C6 | 168.84 (11) |
C16—C17—C18—C19 | 0.8 (3) | O2—K1—O4—C6 | −44.48 (12) |
C17—C18—C19—C14 | 0.5 (3) | C28ii—K1—O4—C6 | −122.39 (12) |
C15—C14—C19—C18 | −1.6 (3) | S1—K1—O4—C6 | 43.92 (11) |
B1—C14—C19—C18 | 177.90 (18) | C29ii—K1—O4—C6 | −105.03 (12) |
C27—C26—B1—N1 | 10.7 (2) | O1—K1—O4—C7 | 113.5 (2) |
C31—C26—B1—N1 | −169.87 (16) | O3—K1—O4—C7 | −154.69 (13) |
C27—C26—B1—C14 | −106.52 (19) | O5—K1—O4—C7 | 18.61 (11) |
C31—C26—B1—C14 | 72.9 (2) | O6—K1—O4—C7 | 37.99 (13) |
C27—C26—B1—C20 | 126.96 (18) | O2—K1—O4—C7 | −175.33 (11) |
C31—C26—B1—C20 | −53.7 (2) | C28ii—K1—O4—C7 | 106.77 (13) |
C15—C14—B1—N1 | −133.09 (18) | S1—K1—O4—C7 | −86.92 (12) |
C19—C14—B1—N1 | 47.5 (2) | C29ii—K1—O4—C7 | 124.13 (13) |
C15—C14—B1—C26 | −15.8 (2) | C10—C9—O5—C8 | 177.26 (15) |
C19—C14—B1—C26 | 164.75 (16) | C10—C9—O5—K1 | 44.63 (17) |
C15—C14—B1—C20 | 109.9 (2) | C7—C8—O5—C9 | 179.18 (15) |
C19—C14—B1—C20 | −69.5 (2) | C7—C8—O5—K1 | −47.25 (18) |
C21—C20—B1—N1 | 11.0 (2) | O4—K1—O5—C9 | 147.18 (13) |
C25—C20—B1—N1 | −173.96 (16) | O1—K1—O5—C9 | −18.34 (13) |
C21—C20—B1—C26 | −105.2 (2) | O3—K1—O5—C9 | 153.93 (11) |
C25—C20—B1—C26 | 69.8 (2) | O6—K1—O5—C9 | −13.21 (11) |
C21—C20—B1—C14 | 128.02 (18) | O2—K1—O5—C9 | 66.4 (2) |
C25—C20—B1—C14 | −57.0 (2) | C28ii—K1—O5—C9 | 55.20 (12) |
C2—C1—O1—C12 | −174.40 (15) | S1—K1—O5—C9 | −116.95 (12) |
C2—C1—O1—K1 | 40.48 (18) | C29ii—K1—O5—C9 | 78.95 (13) |
C11—C12—O1—C1 | 176.44 (15) | O4—K1—O5—C8 | 15.78 (11) |
C11—C12—O1—K1 | −39.22 (18) | O1—K1—O5—C8 | −149.73 (12) |
O4—K1—O1—C1 | 68.6 (2) | O3—K1—O5—C8 | 22.54 (13) |
O3—K1—O1—C1 | −15.91 (13) | O6—K1—O5—C8 | −144.61 (13) |
O5—K1—O1—C1 | 156.46 (11) | O2—K1—O5—C8 | −65.0 (2) |
O6—K1—O1—C1 | 151.27 (13) | C28ii—K1—O5—C8 | −76.19 (12) |
O2—K1—O1—C1 | −9.01 (11) | S1—K1—O5—C8 | 111.65 (12) |
C28ii—K1—O1—C1 | 75.60 (12) | C29ii—K1—O5—C8 | −52.44 (12) |
S1—K1—O1—C1 | −91.58 (12) | C9—C10—O6—C11 | −177.86 (15) |
C29ii—K1—O1—C1 | 58.45 (12) | C9—C10—O6—K1 | 51.86 (17) |
O4—K1—O1—C12 | −73.4 (2) | C12—C11—O6—C10 | 175.70 (15) |
O3—K1—O1—C12 | −157.95 (11) | C12—C11—O6—K1 | −54.27 (17) |
O5—K1—O1—C12 | 14.42 (13) | O4—K1—O6—C10 | −40.46 (13) |
O6—K1—O1—C12 | 9.23 (11) | O1—K1—O6—C10 | 153.83 (13) |
O2—K1—O1—C12 | −151.06 (13) | O3—K1—O6—C10 | −120.0 (2) |
C28ii—K1—O1—C12 | −66.45 (12) | O5—K1—O6—C10 | −20.96 (11) |
S1—K1—O1—C12 | 126.37 (11) | O2—K1—O6—C10 | 172.97 (11) |
C29ii—K1—O1—C12 | −83.60 (12) | C28ii—K1—O6—C10 | −121.11 (13) |
C1—C2—O2—C3 | 179.59 (15) | S1—K1—O6—C10 | 81.06 (12) |
C1—C2—O2—K1 | 56.35 (16) | C29ii—K1—O6—C10 | −114.32 (12) |
C4—C3—O2—C2 | −178.35 (15) | O4—K1—O6—C11 | −170.00 (11) |
C4—C3—O2—K1 | −55.95 (16) | O1—K1—O6—C11 | 24.30 (11) |
O4—K1—O2—C2 | 168.82 (10) | O3—K1—O6—C11 | 110.5 (2) |
O1—K1—O2—C2 | −24.98 (10) | O5—K1—O6—C11 | −150.50 (13) |
O3—K1—O2—C2 | 148.05 (12) | O2—K1—O6—C11 | 43.43 (12) |
O5—K1—O2—C2 | −116.9 (2) | C28ii—K1—O6—C11 | 109.35 (12) |
O6—K1—O2—C2 | −43.88 (12) | S1—K1—O6—C11 | −48.48 (12) |
C28ii—K1—O2—C2 | −105.48 (11) | C29ii—K1—O6—C11 | 116.14 (12) |
S1—K1—O2—C2 | 66.27 (11) | O4—K1—S1—C13 | 148.19 (7) |
C29ii—K1—O2—C2 | −130.01 (11) | O1—K1—S1—C13 | −36.20 (7) |
O4—K1—O2—C3 | 46.03 (12) | O3—K1—S1—C13 | −156.95 (7) |
O1—K1—O2—C3 | −147.76 (12) | O5—K1—S1—C13 | 84.14 (8) |
O3—K1—O2—C3 | 25.27 (11) | O6—K1—S1—C13 | 18.99 (8) |
O5—K1—O2—C3 | 120.29 (19) | O2—K1—S1—C13 | −96.60 (8) |
O6—K1—O2—C3 | −166.67 (11) | C28ii—K1—S1—C13 | −73.37 (13) |
C28ii—K1—O2—C3 | 131.74 (12) | C29ii—K1—S1—C13 | −129.01 (10) |
Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) −x+2, y−1/2, −z+1/2. |
C31H39BKNO6S | F(000) = 1280 |
Mr = 603.6 | Dx = 1.26 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 11.0652 (15) Å | θ = 2–12° |
b = 11.7696 (19) Å | µ = 0.28 mm−1 |
c = 24.424 (4) Å | T = 293 K |
V = 3180.8 (8) Å3 | Rhomb, colorless |
Z = 4 | 0.53 × 0.33 × 0.22 mm |
Enraf Nonius CAD4 diffractometer | θmax = 25.0°, θmin = 2.0° |
non–profiled ω/2θ scans | h = −13→1 |
13000 measured reflections | k = −13→13 |
5586 independent reflections | l = −29→29 |
4976 reflections with I > 2σ(I) | 3 standard reflections every 143 reflections |
Rint = 0.027 | intensity decay: 11% |
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0501P)2 + 0.5418P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.032 | (Δ/σ)max = 0.03 |
wR(F2) = 0.094 | Δρmax = 0.28 e Å−3 |
S = 1.07 | Δρmin = −0.27 e Å−3 |
5586 reflections | Absolute structure: Flack (1983); 2428 Friedel pairs. |
370 parameters | Absolute structure parameter: 0.01 (4) |
33 restraints |
C31H39BKNO6S | V = 3180.8 (8) Å3 |
Mr = 603.6 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 11.0652 (15) Å | µ = 0.28 mm−1 |
b = 11.7696 (19) Å | T = 293 K |
c = 24.424 (4) Å | 0.53 × 0.33 × 0.22 mm |
Enraf Nonius CAD4 diffractometer | Rint = 0.027 |
13000 measured reflections | 3 standard reflections every 143 reflections |
5586 independent reflections | intensity decay: 11% |
4976 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.094 | Δρmax = 0.28 e Å−3 |
S = 1.07 | Δρmin = −0.27 e Å−3 |
5586 reflections | Absolute structure: Flack (1983); 2428 Friedel pairs. |
370 parameters | Absolute structure parameter: 0.01 (4) |
33 restraints |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 1.6430 (0.0028) x + 10.5790 (0.0022) y - 10.0715 (0.0063) z = 1.5956 (0.0028) * 0.2672 (0.0008) K1 * 0.1227 (0.0016) O1 * -0.2582 (0.0016) O2 * 0.1693 (0.0016) O3 * -0.1621 (0.0017) O4 * 0.2030 (0.0017) O5 * -0.1582 (0.0017) O6 * -0.3242 (0.0025) C1 * 0.2678 (0.0025) C2 * 0.2790 (0.0024) C3 * -0.2561 (0.0024) C4 * -0.2876 (0.0024) C5 * 0.3059 (0.0024) C6 * 0.2100 (0.0027) C7 * -0.3756 (0.0027) C8 * -0.3050 (0.0024) C9 * 0.2736 (0.0025) C10 * 0.3111 (0.0026) C11 * -0.2823 (0.0024) C12 3.4195 (0.0011) S1 Rms deviation of fitted atoms = 0.2616 4.3619 (0.0112) x + 4.3697 (0.0112) y - 20.5331 (0.0146) z = 5.1078 (0.0126) Angle to [K(18-crown-6)]+ plane (with approximate e.s.d.) = 42.36 (0.07) * 0.0098 (0.0017) C14 * -0.0075 (0.0017) C15 * -0.0008 (0.0018) C16 * 0.0069 (0.0019) C17 * -0.0043 (0.0021) C18 * -0.0041 (0.0020) C19 Rms deviation of fitted atoms = 0.0063 5.7803 (0.0120) x + 6.4472 (0.0115) y + 15.9609 (0.0217) z = 10.2487 (0.0119) Angle to [K(18-crown-6)]+ plane (with approximate e.s.d.) = 72.51 (0.06) * 0.0250 (0.0017) C20 * -0.0069 (0.0020) C21 * -0.0148 (0.0024) C22 * 0.0184 (0.0023) C23 * 0.0006 (0.0021) C24 * -0.0224 (0.0019) C25 Rms deviation of fitted atoms = 0.0170 -2.0127 (0.0098) x + 11.5198 (0.0028) y - 2.3052 (0.0229) z = 3.1722 (0.0135) Angle to [K(18-crown-6)]+ (with approximate e.s.d.) = 26.92 (0.05) * -0.0053 (0.0015) C26 * 0.0081 (0.0015) C27 * -0.0042 (0.0015) C28 * -0.0026 (0.0016) C29 * 0.0052 (0.0017) C30 * -0.0013 (0.0017) C31 Rms deviation of fitted atoms = 0.0050 |
x | y | z | Uiso*/Ueq | ||
C20 | 1.0687 (2) | 0.56794 (18) | 0.02724 (9) | 0.0494 (5) | |
C21 | 0.9821 (3) | 0.6530 (2) | 0.02223 (11) | 0.0695 (7) | |
H21 | 0.9157 | 0.6523 | 0.0455 | 0.083* | |
C22 | 0.9916 (4) | 0.7387 (3) | −0.01633 (13) | 0.0926 (11) | |
H22 | 0.9318 | 0.7939 | −0.0187 | 0.111* | |
C23 | 1.0882 (4) | 0.7426 (3) | −0.05080 (13) | 0.0911 (10) | |
H23 | 1.0963 | 0.8021 | −0.0756 | 0.109* | |
C24 | 1.1730 (3) | 0.6587 (3) | −0.04876 (11) | 0.0821 (8) | |
H24 | 1.2384 | 0.6598 | −0.0727 | 0.099* | |
C25 | 1.1613 (2) | 0.5715 (2) | −0.01072 (10) | 0.0624 (6) | |
H25 | 1.218 | 0.5132 | −0.0108 | 0.075* | |
C26 | 1.17418 (18) | 0.50439 (17) | 0.12155 (8) | 0.0443 (4) | |
C27 | 1.1533 (2) | 0.51307 (17) | 0.17734 (9) | 0.0519 (4) | |
H27 | 1.075 | 0.5035 | 0.1903 | 0.062* | |
C28 | 1.2457 (2) | 0.53564 (18) | 0.21479 (10) | 0.0617 (5) | |
H28 | 1.2285 | 0.5393 | 0.252 | 0.074* | |
C29 | 1.3576 (2) | 0.55185 (19) | 0.19745 (11) | 0.0622 (5) | |
H29 | 1.4183 | 0.5671 | 0.2228 | 0.075* | |
C30 | 1.3855 (2) | 0.5466 (2) | 0.14354 (12) | 0.0642 (6) | |
H30 | 1.4644 | 0.5589 | 0.1318 | 0.077* | |
C31 | 1.2951 (2) | 0.5228 (2) | 0.10601 (10) | 0.0575 (5) | |
H31 | 1.3152 | 0.5187 | 0.0691 | 0.069* | |
C1 | 0.7838 (2) | 0.1155 (2) | 0.12299 (10) | 0.0664 (7) | |
H1A | 0.7654 | 0.0427 | 0.1396 | 0.08* | |
H1B | 0.8244 | 0.1019 | 0.0884 | 0.08* | |
C2 | 0.6705 (3) | 0.1801 (2) | 0.11360 (10) | 0.0712 (7) | |
H2A | 0.6895 | 0.2556 | 0.1001 | 0.085* | |
H2B | 0.6216 | 0.1418 | 0.0863 | 0.085* | |
C3 | 0.4962 (2) | 0.2496 (2) | 0.15705 (12) | 0.0679 (7) | |
H3A | 0.4447 | 0.2107 | 0.1309 | 0.081* | |
H3B | 0.5137 | 0.3248 | 0.1428 | 0.081* | |
C4 | 0.4330 (2) | 0.2595 (2) | 0.21027 (12) | 0.0680 (7) | |
H4A | 0.3558 | 0.2972 | 0.2052 | 0.082* | |
H4B | 0.4181 | 0.1845 | 0.2253 | 0.082* | |
C5 | 0.4520 (2) | 0.3377 (2) | 0.29855 (12) | 0.0700 (7) | |
H5A | 0.4433 | 0.2646 | 0.3165 | 0.084* | |
H5B | 0.3723 | 0.3709 | 0.2944 | 0.084* | |
C6 | 0.5296 (2) | 0.4135 (2) | 0.33193 (12) | 0.0722 (7) | |
H6A | 0.5415 | 0.4851 | 0.3131 | 0.087* | |
H6B | 0.491 | 0.429 | 0.3668 | 0.087* | |
C7 | 0.7169 (3) | 0.4191 (2) | 0.37787 (12) | 0.0790 (8) | |
H7A | 0.6755 | 0.4281 | 0.4126 | 0.095* | |
H7B | 0.7354 | 0.494 | 0.3636 | 0.095* | |
C8 | 0.8305 (3) | 0.3538 (3) | 0.38599 (11) | 0.0770 (8) | |
H8A | 0.879 | 0.3895 | 0.4142 | 0.092* | |
H8B | 0.8116 | 0.2771 | 0.3977 | 0.092* | |
C9 | 1.0067 (2) | 0.2901 (2) | 0.34081 (12) | 0.0720 (7) | |
H9A | 0.9907 | 0.2139 | 0.3541 | 0.086* | |
H9B | 1.0586 | 0.3279 | 0.3671 | 0.086* | |
C10 | 1.0687 (2) | 0.2839 (2) | 0.28698 (12) | 0.0713 (7) | |
H10A | 1.0805 | 0.3598 | 0.2725 | 0.086* | |
H10B | 1.1473 | 0.2485 | 0.2912 | 0.086* | |
C11 | 1.0516 (2) | 0.2058 (3) | 0.19845 (12) | 0.0708 (7) | |
H11A | 1.1316 | 0.1732 | 0.2025 | 0.085* | |
H11B | 1.0596 | 0.2791 | 0.1806 | 0.085* | |
C12 | 0.9748 (2) | 0.1296 (2) | 0.16474 (12) | 0.0658 (6) | |
H12A | 1.012 | 0.1178 | 0.1292 | 0.079* | |
H12B | 0.9669 | 0.0563 | 0.1826 | 0.079* | |
C13 | 0.8567 (2) | 0.49654 (19) | 0.13084 (10) | 0.0542 (5) | |
C14 | 1.07982 (18) | 0.34513 (18) | 0.05360 (8) | 0.0480 (5) | |
C15 | 1.1799 (2) | 0.2760 (2) | 0.06099 (11) | 0.0606 (6) | |
H15 | 1.2449 | 0.303 | 0.0813 | 0.073* | |
C16 | 1.1859 (3) | 0.1671 (2) | 0.03876 (12) | 0.0730 (7) | |
H16 | 1.2547 | 0.123 | 0.044 | 0.088* | |
C17 | 1.0914 (3) | 0.1250 (2) | 0.00934 (12) | 0.0789 (9) | |
H17 | 1.0957 | 0.0525 | −0.0058 | 0.095* | |
C18 | 0.9900 (3) | 0.1897 (3) | 0.00214 (12) | 0.0817 (9) | |
H18 | 0.9247 | 0.1611 | −0.0175 | 0.098* | |
C19 | 0.9851 (3) | 0.2981 (2) | 0.02414 (11) | 0.0678 (6) | |
H19 | 0.9155 | 0.341 | 0.0189 | 0.081* | |
B1 | 1.0700 (2) | 0.4743 (2) | 0.07685 (10) | 0.0471 (5) | |
K1 | 0.75496 (4) | 0.29219 (4) | 0.24512 (2) | 0.05503 (13) | |
N1 | 0.94531 (16) | 0.48313 (17) | 0.10710 (8) | 0.0558 (4) | |
O1 | 0.85944 (14) | 0.17942 (13) | 0.15806 (7) | 0.0599 (4) | |
O2 | 0.60550 (14) | 0.18827 (13) | 0.16375 (7) | 0.0576 (4) | |
O3 | 0.50607 (14) | 0.32322 (13) | 0.24683 (7) | 0.0610 (4) | |
O4 | 0.64182 (16) | 0.36010 (14) | 0.34062 (7) | 0.0659 (4) | |
O5 | 0.89621 (15) | 0.35072 (14) | 0.33601 (7) | 0.0643 (4) | |
O6 | 0.99713 (14) | 0.21968 (14) | 0.25070 (8) | 0.0622 (4) | |
S1 | 0.73263 (6) | 0.51686 (6) | 0.16448 (3) | 0.0803 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C20 | 0.0544 (12) | 0.0432 (11) | 0.0507 (12) | 0.0022 (9) | −0.0093 (10) | −0.0022 (9) |
C21 | 0.0817 (18) | 0.0672 (16) | 0.0596 (15) | 0.0233 (14) | −0.0096 (13) | 0.0023 (12) |
C22 | 0.131 (3) | 0.0686 (18) | 0.078 (2) | 0.0351 (19) | −0.021 (2) | 0.0113 (16) |
C23 | 0.147 (3) | 0.0643 (17) | 0.0619 (18) | −0.004 (2) | −0.021 (2) | 0.0180 (14) |
C24 | 0.099 (2) | 0.090 (2) | 0.0581 (16) | −0.0160 (18) | 0.0015 (14) | 0.0153 (14) |
C25 | 0.0657 (15) | 0.0634 (14) | 0.0583 (14) | 0.0007 (12) | −0.0005 (11) | 0.0069 (11) |
C26 | 0.0506 (9) | 0.0343 (9) | 0.0481 (9) | 0.0046 (8) | −0.0021 (8) | 0.0033 (8) |
C27 | 0.0611 (11) | 0.0394 (10) | 0.0553 (10) | 0.0050 (9) | 0.0007 (8) | −0.0006 (9) |
C28 | 0.0878 (13) | 0.0455 (11) | 0.0519 (11) | 0.0021 (13) | −0.0125 (10) | −0.0027 (9) |
C29 | 0.0756 (12) | 0.0392 (11) | 0.0717 (12) | −0.0005 (11) | −0.0252 (11) | −0.0005 (10) |
C30 | 0.0507 (11) | 0.0555 (13) | 0.0863 (14) | −0.0072 (10) | −0.0114 (10) | 0.0122 (12) |
C31 | 0.0529 (10) | 0.0605 (13) | 0.0590 (12) | −0.0026 (10) | −0.0021 (8) | 0.0073 (11) |
C1 | 0.0800 (17) | 0.0660 (15) | 0.0532 (14) | −0.0004 (13) | 0.0090 (12) | −0.0119 (11) |
C2 | 0.0888 (18) | 0.0742 (17) | 0.0505 (14) | −0.0001 (14) | −0.0067 (12) | −0.0025 (12) |
C3 | 0.0646 (14) | 0.0556 (13) | 0.0834 (18) | 0.0044 (11) | −0.0207 (14) | 0.0016 (12) |
C4 | 0.0499 (12) | 0.0530 (13) | 0.101 (2) | 0.0025 (11) | −0.0095 (13) | 0.0024 (13) |
C5 | 0.0591 (14) | 0.0593 (14) | 0.091 (2) | 0.0091 (12) | 0.0206 (13) | 0.0080 (13) |
C6 | 0.0829 (18) | 0.0510 (13) | 0.0827 (19) | 0.0145 (12) | 0.0267 (15) | −0.0008 (12) |
C7 | 0.102 (2) | 0.0613 (15) | 0.0733 (18) | −0.0118 (15) | 0.0108 (15) | −0.0210 (13) |
C8 | 0.099 (2) | 0.0717 (17) | 0.0607 (16) | −0.0164 (16) | −0.0073 (14) | −0.0046 (13) |
C9 | 0.0768 (16) | 0.0603 (14) | 0.0788 (17) | −0.0157 (13) | −0.0284 (14) | 0.0070 (13) |
C10 | 0.0559 (13) | 0.0635 (15) | 0.094 (2) | −0.0127 (12) | −0.0122 (13) | 0.0054 (14) |
C11 | 0.0542 (13) | 0.0654 (15) | 0.093 (2) | −0.0004 (12) | 0.0182 (13) | 0.0023 (14) |
C12 | 0.0613 (14) | 0.0576 (14) | 0.0783 (17) | 0.0049 (11) | 0.0214 (12) | −0.0027 (12) |
C13 | 0.0468 (10) | 0.0469 (12) | 0.0691 (14) | 0.0008 (10) | −0.0004 (9) | 0.0068 (10) |
C14 | 0.0482 (11) | 0.0476 (11) | 0.0483 (12) | −0.0028 (9) | 0.0030 (9) | 0.0066 (9) |
C15 | 0.0580 (13) | 0.0498 (13) | 0.0739 (16) | −0.0016 (11) | 0.0062 (11) | 0.0052 (11) |
C16 | 0.0852 (18) | 0.0488 (13) | 0.0849 (19) | 0.0086 (13) | 0.0244 (15) | 0.0075 (12) |
C17 | 0.119 (3) | 0.0462 (13) | 0.0712 (17) | −0.0137 (16) | 0.0230 (17) | −0.0036 (12) |
C18 | 0.103 (2) | 0.0687 (18) | 0.0736 (18) | −0.0256 (17) | −0.0089 (16) | −0.0076 (14) |
C19 | 0.0747 (16) | 0.0585 (14) | 0.0701 (16) | −0.0044 (13) | −0.0124 (13) | −0.0037 (12) |
B1 | 0.0432 (12) | 0.0482 (12) | 0.0500 (13) | 0.0020 (10) | 0.0001 (10) | 0.0019 (10) |
K1 | 0.0523 (2) | 0.0524 (2) | 0.0604 (3) | 0.0038 (2) | −0.0002 (2) | −0.0065 (2) |
N1 | 0.0471 (9) | 0.0585 (11) | 0.0617 (11) | 0.0016 (9) | 0.0024 (8) | 0.0016 (9) |
O1 | 0.0639 (9) | 0.0523 (9) | 0.0636 (10) | 0.0035 (7) | 0.0070 (8) | −0.0058 (7) |
O2 | 0.0612 (9) | 0.0511 (9) | 0.0604 (9) | 0.0050 (7) | −0.0068 (7) | 0.0028 (7) |
O3 | 0.0508 (8) | 0.0560 (9) | 0.0762 (10) | 0.0025 (7) | 0.0068 (8) | 0.0023 (8) |
O4 | 0.0765 (11) | 0.0504 (9) | 0.0709 (11) | 0.0015 (8) | 0.0084 (9) | −0.0110 (8) |
O5 | 0.0738 (11) | 0.0532 (9) | 0.0658 (10) | −0.0091 (8) | −0.0103 (8) | 0.0036 (8) |
O6 | 0.0525 (8) | 0.0583 (9) | 0.0759 (10) | −0.0083 (7) | 0.0015 (8) | 0.0038 (9) |
S1 | 0.0552 (3) | 0.0721 (4) | 0.1136 (6) | 0.0114 (3) | 0.0274 (4) | 0.0166 (4) |
C20—C25 | 1.383 (3) | C6—H6B | 0.97 |
C20—C21 | 1.391 (3) | C7—O4 | 1.414 (3) |
C20—B1 | 1.638 (3) | C7—C8 | 1.486 (4) |
C21—C22 | 1.384 (4) | C7—H7A | 0.97 |
C21—H21 | 0.93 | C7—H7B | 0.97 |
C22—C23 | 1.361 (5) | C8—O5 | 1.421 (3) |
C22—H22 | 0.93 | C8—H8A | 0.97 |
C23—C24 | 1.362 (5) | C8—H8B | 0.97 |
C23—H23 | 0.93 | C9—O5 | 1.420 (3) |
C24—C25 | 1.391 (4) | C9—C10 | 1.485 (4) |
C24—H24 | 0.93 | C9—H9A | 0.97 |
C25—H25 | 0.93 | C9—H9B | 0.97 |
C26—C27 | 1.386 (3) | C10—O6 | 1.408 (3) |
C26—C31 | 1.408 (3) | C10—H10A | 0.97 |
C26—B1 | 1.627 (3) | C10—H10B | 0.97 |
C27—C28 | 1.397 (3) | C11—O6 | 1.421 (3) |
C27—H27 | 0.93 | C11—C12 | 1.485 (4) |
C28—C29 | 1.323 (4) | C11—H11A | 0.97 |
C28—K1i | 3.174 (2) | C11—H11B | 0.97 |
C28—H28 | 0.93 | C12—O1 | 1.414 (3) |
C29—C30 | 1.354 (4) | C12—H12A | 0.97 |
C29—K1i | 3.394 (3) | C12—H12B | 0.97 |
C29—H29 | 0.93 | C13—N1 | 1.150 (3) |
C30—C31 | 1.385 (3) | C13—S1 | 1.617 (2) |
C30—H30 | 0.93 | C14—C15 | 1.387 (3) |
C31—H31 | 0.93 | C14—C19 | 1.387 (3) |
C1—O1 | 1.414 (3) | C14—B1 | 1.626 (3) |
C1—C2 | 1.484 (4) | C15—C16 | 1.394 (4) |
C1—H1A | 0.97 | C15—H15 | 0.93 |
C1—H1B | 0.97 | C16—C17 | 1.363 (4) |
C2—O2 | 1.424 (3) | C16—H16 | 0.93 |
C2—H2A | 0.97 | C17—C18 | 1.367 (4) |
C2—H2B | 0.97 | C17—H17 | 0.93 |
C3—O2 | 1.418 (3) | C18—C19 | 1.385 (4) |
C3—C4 | 1.481 (4) | C18—H18 | 0.93 |
C3—H3A | 0.97 | C19—H19 | 0.93 |
C3—H3B | 0.97 | B1—N1 | 1.568 (3) |
C4—O3 | 1.419 (3) | K1—O1 | 2.7604 (16) |
C4—H4A | 0.97 | K1—O4 | 2.7651 (17) |
C4—H4B | 0.97 | K1—O3 | 2.7784 (16) |
C5—O3 | 1.408 (3) | K1—O5 | 2.8010 (17) |
C5—C6 | 1.483 (4) | K1—O6 | 2.8156 (17) |
C5—H5A | 0.97 | K1—O2 | 2.8602 (17) |
C5—H5B | 0.97 | K1—C28ii | 3.174 (2) |
C6—O4 | 1.408 (3) | K1—S1 | 3.3064 (10) |
C6—H6A | 0.97 | K1—C29ii | 3.394 (3) |
C25—C20—C21 | 115.4 (2) | C9—C10—H10A | 109.9 |
C25—C20—B1 | 120.66 (19) | O6—C10—H10B | 109.9 |
C21—C20—B1 | 123.7 (2) | C9—C10—H10B | 109.9 |
C22—C21—C20 | 122.1 (3) | H10A—C10—H10B | 108.3 |
C22—C21—H21 | 118.9 | O6—C11—C12 | 108.9 (2) |
C20—C21—H21 | 118.9 | O6—C11—H11A | 109.9 |
C23—C22—C21 | 120.3 (3) | C12—C11—H11A | 109.9 |
C23—C22—H22 | 119.8 | O6—C11—H11B | 109.9 |
C21—C22—H22 | 119.8 | C12—C11—H11B | 109.9 |
C22—C23—C24 | 119.6 (3) | H11A—C11—H11B | 108.3 |
C22—C23—H23 | 120.2 | O1—C12—C11 | 109.3 (2) |
C24—C23—H23 | 120.2 | O1—C12—H12A | 109.8 |
C23—C24—C25 | 119.6 (3) | C11—C12—H12A | 109.8 |
C23—C24—H24 | 120.2 | O1—C12—H12B | 109.8 |
C25—C24—H24 | 120.2 | C11—C12—H12B | 109.8 |
C20—C25—C24 | 122.7 (3) | H12A—C12—H12B | 108.3 |
C20—C25—H25 | 118.7 | N1—C13—S1 | 179.3 (2) |
C24—C25—H25 | 118.7 | C15—C14—C19 | 115.9 (2) |
C27—C26—C31 | 114.3 (2) | C15—C14—B1 | 123.8 (2) |
C27—C26—B1 | 123.91 (19) | C19—C14—B1 | 120.3 (2) |
C31—C26—B1 | 121.75 (19) | C14—C15—C16 | 121.8 (3) |
C26—C27—C28 | 122.4 (2) | C14—C15—H15 | 119.1 |
C26—C27—H27 | 118.8 | C16—C15—H15 | 119.1 |
C28—C27—H27 | 118.8 | C17—C16—C15 | 120.2 (3) |
C29—C28—C27 | 120.2 (2) | C17—C16—H16 | 119.9 |
C29—C28—K1i | 87.92 (14) | C15—C16—H16 | 119.9 |
C27—C28—K1i | 112.40 (14) | C16—C17—C18 | 119.7 (3) |
C29—C28—H28 | 119.9 | C16—C17—H17 | 120.2 |
C27—C28—H28 | 119.9 | C18—C17—H17 | 120.2 |
K1i—C28—H28 | 69.8 | C17—C18—C19 | 119.7 (3) |
C28—C29—C30 | 121.2 (2) | C17—C18—H18 | 120.1 |
C28—C29—K1i | 69.16 (14) | C19—C18—H18 | 120.1 |
C30—C29—K1i | 121.56 (16) | C18—C19—C14 | 122.6 (3) |
C28—C29—H29 | 119.4 | C18—C19—H19 | 118.7 |
C30—C29—H29 | 119.4 | C14—C19—H19 | 118.7 |
K1i—C29—H29 | 80.2 | N1—B1—C14 | 106.59 (17) |
C29—C30—C31 | 119.3 (2) | N1—B1—C26 | 107.02 (17) |
C29—C30—H30 | 120.4 | C14—B1—C26 | 112.99 (17) |
C31—C30—H30 | 120.4 | N1—B1—C20 | 107.22 (17) |
C30—C31—C26 | 122.6 (2) | C14—B1—C20 | 111.79 (18) |
C30—C31—H31 | 118.7 | C26—B1—C20 | 110.85 (18) |
C26—C31—H31 | 118.7 | O1—K1—O4 | 168.06 (5) |
O1—C1—C2 | 108.7 (2) | O1—K1—O3 | 119.33 (5) |
O1—C1—H1A | 109.9 | O4—K1—O3 | 60.04 (5) |
C2—C1—H1A | 109.9 | O1—K1—O5 | 119.68 (5) |
O1—C1—H1B | 109.9 | O4—K1—O5 | 60.86 (5) |
C2—C1—H1B | 109.9 | O3—K1—O5 | 120.59 (6) |
H1A—C1—H1B | 108.3 | O1—K1—O6 | 59.53 (5) |
O2—C2—C1 | 109.2 (2) | O4—K1—O6 | 118.53 (6) |
O2—C2—H2A | 109.8 | O3—K1—O6 | 169.26 (5) |
C1—C2—H2A | 109.8 | O5—K1—O6 | 60.34 (5) |
O2—C2—H2B | 109.8 | O1—K1—O2 | 60.09 (5) |
C1—C2—H2B | 109.8 | O4—K1—O2 | 116.61 (5) |
H2A—C2—H2B | 108.3 | O3—K1—O2 | 59.57 (5) |
O2—C3—C4 | 110.0 (2) | O5—K1—O2 | 168.10 (5) |
O2—C3—H3A | 109.7 | O6—K1—O2 | 117.02 (5) |
C4—C3—H3A | 109.7 | O1—K1—C28ii | 77.36 (6) |
O2—C3—H3B | 109.7 | O4—K1—C28ii | 90.79 (6) |
C4—C3—H3B | 109.7 | O3—K1—C28ii | 96.78 (6) |
H3A—C3—H3B | 108.2 | O5—K1—C28ii | 89.47 (5) |
O3—C4—C3 | 109.0 (2) | O6—K1—C28ii | 72.48 (6) |
O3—C4—H4A | 109.9 | O2—K1—C28ii | 78.82 (5) |
C3—C4—H4A | 109.9 | O1—K1—S1 | 87.53 (4) |
O3—C4—H4B | 109.9 | O4—K1—S1 | 103.74 (4) |
C3—C4—H4B | 109.9 | O3—K1—S1 | 80.20 (4) |
H4A—C4—H4B | 108.3 | O5—K1—S1 | 108.49 (4) |
O3—C5—C6 | 108.6 (2) | O6—K1—S1 | 110.02 (4) |
O3—C5—H5A | 110 | O2—K1—S1 | 83.39 (4) |
C6—C5—H5A | 110 | C28ii—K1—S1 | 160.79 (5) |
O3—C5—H5B | 110 | O1—K1—C29ii | 94.09 (6) |
C6—C5—H5B | 110 | O4—K1—C29ii | 74.11 (6) |
H5A—C5—H5B | 108.3 | O3—K1—C29ii | 74.90 (6) |
O4—C6—C5 | 109.0 (2) | O5—K1—C29ii | 94.72 (6) |
O4—C6—H6A | 109.9 | O6—K1—C29ii | 94.40 (6) |
C5—C6—H6A | 109.9 | O2—K1—C29ii | 73.65 (5) |
O4—C6—H6B | 109.9 | C28ii—K1—C29ii | 22.92 (6) |
C5—C6—H6B | 109.9 | S1—K1—C29ii | 152.28 (5) |
H6A—C6—H6B | 108.3 | C13—N1—B1 | 175.3 (2) |
O4—C7—C8 | 109.2 (2) | C12—O1—C1 | 112.55 (18) |
O4—C7—H7A | 109.8 | C12—O1—K1 | 119.25 (15) |
C8—C7—H7A | 109.8 | C1—O1—K1 | 118.32 (13) |
O4—C7—H7B | 109.8 | C3—O2—C2 | 111.46 (19) |
C8—C7—H7B | 109.8 | C3—O2—K1 | 110.83 (13) |
H7A—C7—H7B | 108.3 | C2—O2—K1 | 109.52 (14) |
O5—C8—C7 | 109.4 (2) | C5—O3—C4 | 112.72 (19) |
O5—C8—H8A | 109.8 | C5—O3—K1 | 116.79 (15) |
C7—C8—H8A | 109.8 | C4—O3—K1 | 119.08 (14) |
O5—C8—H8B | 109.8 | C6—O4—C7 | 113.3 (2) |
C7—C8—H8B | 109.8 | C6—O4—K1 | 113.66 (15) |
H8A—C8—H8B | 108.3 | C7—O4—K1 | 114.75 (16) |
O5—C9—C10 | 110.4 (2) | C9—O5—C8 | 112.5 (2) |
O5—C9—H9A | 109.6 | C9—O5—K1 | 114.97 (14) |
C10—C9—H9A | 109.6 | C8—O5—K1 | 113.67 (15) |
O5—C9—H9B | 109.6 | C10—O6—C11 | 112.85 (19) |
C10—C9—H9B | 109.6 | C10—O6—K1 | 113.74 (15) |
H9A—C9—H9B | 108.1 | C11—O6—K1 | 113.27 (15) |
O6—C10—C9 | 108.9 (2) | C13—S1—K1 | 96.95 (9) |
O6—C10—H10A | 109.9 | ||
C25—C20—C21—C22 | −3.2 (4) | S1—K1—O2—C2 | 65.89 (14) |
B1—C20—C21—C22 | 172.2 (3) | C29ii—K1—O2—C2 | −129.81 (15) |
C20—C21—C22—C23 | −0.5 (5) | C6—C5—O3—C4 | −175.0 (2) |
C21—C22—C23—C24 | 2.8 (5) | C6—C5—O3—K1 | 41.8 (2) |
C22—C23—C24—C25 | −1.4 (5) | C3—C4—O3—C5 | 179.46 (19) |
C21—C20—C25—C24 | 4.8 (4) | C3—C4—O3—K1 | −38.2 (2) |
B1—C20—C25—C24 | −170.8 (2) | O1—K1—O3—C5 | 155.18 (15) |
C23—C24—C25—C20 | −2.6 (4) | O4—K1—O3—C5 | −11.09 (15) |
C31—C26—C27—C28 | −1.4 (3) | O5—K1—O3—C5 | −17.51 (17) |
B1—C26—C27—C28 | 177.98 (19) | O6—K1—O3—C5 | 74.3 (4) |
C26—C27—C28—C29 | 1.4 (3) | O2—K1—O3—C5 | 148.67 (17) |
C26—C27—C28—K1i | 102.6 (2) | C28ii—K1—O3—C5 | 75.90 (16) |
C27—C28—C29—C30 | −0.3 (3) | S1—K1—O3—C5 | −123.28 (16) |
K1i—C28—C29—C30 | −115.1 (2) | C29ii—K1—O3—C5 | 69.02 (16) |
C27—C28—C29—K1i | 114.8 (2) | O1—K1—O3—C4 | 14.30 (18) |
C28—C29—C30—C31 | −0.6 (4) | O4—K1—O3—C4 | −151.97 (18) |
K1i—C29—C30—C31 | −84.0 (3) | O5—K1—O3—C4 | −158.39 (16) |
C29—C30—C31—C26 | 0.5 (4) | O6—K1—O3—C4 | −66.6 (4) |
C27—C26—C31—C30 | 0.5 (3) | O2—K1—O3—C4 | 7.79 (16) |
B1—C26—C31—C30 | −178.9 (2) | C28ii—K1—O3—C4 | −64.98 (17) |
O1—C1—C2—O2 | −66.1 (3) | S1—K1—O3—C4 | 95.84 (17) |
O2—C3—C4—O3 | 63.2 (2) | C29ii—K1—O3—C4 | −71.86 (17) |
O3—C5—C6—O4 | −63.7 (3) | C5—C6—O4—C7 | −172.4 (2) |
O4—C7—C8—O5 | 65.2 (3) | C5—C6—O4—K1 | 54.3 (2) |
O5—C9—C10—O6 | −64.7 (3) | C8—C7—O4—C6 | 177.7 (2) |
O6—C11—C12—O1 | 60.9 (3) | C8—C7—O4—K1 | −49.5 (3) |
C19—C14—C15—C16 | 1.8 (3) | O1—K1—O4—C6 | −113.4 (3) |
B1—C14—C15—C16 | −177.8 (2) | O3—K1—O4—C6 | −23.03 (15) |
C14—C15—C16—C17 | −0.8 (4) | O5—K1—O4—C6 | 150.63 (17) |
C15—C16—C17—C18 | −0.6 (4) | O6—K1—O4—C6 | 169.17 (15) |
C16—C17—C18—C19 | 0.9 (4) | O2—K1—O4—C6 | −42.53 (16) |
C17—C18—C19—C14 | 0.1 (5) | C28ii—K1—O4—C6 | −120.41 (16) |
C15—C14—C19—C18 | −1.4 (4) | S1—K1—O4—C6 | 46.89 (16) |
B1—C14—C19—C18 | 178.2 (3) | C29ii—K1—O4—C6 | −104.50 (16) |
C15—C14—B1—N1 | −130.9 (2) | O1—K1—O4—C7 | 113.9 (3) |
C19—C14—B1—N1 | 49.5 (3) | O3—K1—O4—C7 | −155.71 (19) |
C15—C14—B1—C26 | −13.7 (3) | O5—K1—O4—C7 | 17.96 (17) |
C19—C14—B1—C26 | 166.8 (2) | O6—K1—O4—C7 | 36.50 (19) |
C15—C14—B1—C20 | 112.2 (2) | O2—K1—O4—C7 | −175.20 (17) |
C19—C14—B1—C20 | −67.4 (3) | C28ii—K1—O4—C7 | 106.91 (18) |
C27—C26—B1—N1 | 11.4 (3) | S1—K1—O4—C7 | −85.78 (18) |
C31—C26—B1—N1 | −169.3 (2) | C29ii—K1—O4—C7 | 122.83 (18) |
C27—C26—B1—C14 | −105.6 (2) | C10—C9—O5—C8 | 176.9 (2) |
C31—C26—B1—C14 | 73.7 (3) | C10—C9—O5—K1 | 44.7 (2) |
C27—C26—B1—C20 | 128.0 (2) | C7—C8—O5—C9 | 179.6 (2) |
C31—C26—B1—C20 | −52.7 (3) | C7—C8—O5—K1 | −47.5 (2) |
C25—C20—B1—N1 | −172.6 (2) | O1—K1—O5—C9 | −18.38 (17) |
C21—C20—B1—N1 | 12.1 (3) | O4—K1—O5—C9 | 147.92 (17) |
C25—C20—B1—C14 | −56.2 (3) | O3—K1—O5—C9 | 154.29 (15) |
C21—C20—B1—C14 | 128.6 (2) | O6—K1—O5—C9 | −13.33 (15) |
C25—C20—B1—C26 | 70.9 (3) | O2—K1—O5—C9 | 67.1 (3) |
C21—C20—B1—C26 | −104.3 (2) | C28ii—K1—O5—C9 | 56.72 (16) |
C11—C12—O1—C1 | 175.7 (2) | S1—K1—O5—C9 | −116.33 (15) |
C11—C12—O1—K1 | −39.1 (2) | C29ii—K1—O5—C9 | 79.06 (16) |
C2—C1—O1—C12 | −173.9 (2) | O1—K1—O5—C8 | −150.04 (16) |
C2—C1—O1—K1 | 40.6 (2) | O4—K1—O5—C8 | 16.26 (16) |
O4—K1—O1—C12 | −75.0 (3) | O3—K1—O5—C8 | 22.63 (18) |
O3—K1—O1—C12 | −158.57 (14) | O6—K1—O5—C8 | −144.99 (18) |
O5—K1—O1—C12 | 14.19 (16) | O2—K1—O5—C8 | −64.6 (3) |
O6—K1—O1—C12 | 9.10 (14) | C28ii—K1—O5—C8 | −74.94 (17) |
O2—K1—O1—C12 | −152.09 (16) | S1—K1—O5—C8 | 112.01 (16) |
C28ii—K1—O1—C12 | −67.84 (15) | C29ii—K1—O5—C8 | −52.61 (17) |
S1—K1—O1—C12 | 124.11 (15) | C9—C10—O6—C11 | −177.9 (2) |
C29ii—K1—O1—C12 | −83.61 (15) | C9—C10—O6—K1 | 51.3 (2) |
O4—K1—O1—C1 | 68.3 (3) | C12—C11—O6—C10 | 175.4 (2) |
O3—K1—O1—C1 | −15.33 (18) | C12—C11—O6—K1 | −53.5 (2) |
O5—K1—O1—C1 | 157.43 (16) | O1—K1—O6—C10 | 154.41 (17) |
O6—K1—O1—C1 | 152.34 (17) | O4—K1—O6—C10 | −39.14 (17) |
O2—K1—O1—C1 | −8.85 (15) | O3—K1—O6—C10 | −118.6 (3) |
C28ii—K1—O1—C1 | 75.40 (17) | O5—K1—O6—C10 | −20.50 (16) |
S1—K1—O1—C1 | −92.64 (16) | O2—K1—O6—C10 | 172.69 (16) |
C29ii—K1—O1—C1 | 59.64 (17) | C28ii—K1—O6—C10 | −120.21 (17) |
C4—C3—O2—C2 | −178.2 (2) | S1—K1—O6—C10 | 79.92 (17) |
C4—C3—O2—K1 | −55.9 (2) | C29ii—K1—O6—C10 | −113.43 (17) |
C1—C2—O2—C3 | 179.9 (2) | O1—K1—O6—C11 | 23.80 (15) |
C1—C2—O2—K1 | 56.9 (2) | O4—K1—O6—C11 | −169.75 (15) |
O1—K1—O2—C3 | −148.45 (16) | O3—K1—O6—C11 | 110.8 (3) |
O4—K1—O2—C3 | 44.59 (16) | O5—K1—O6—C11 | −151.11 (17) |
O3—K1—O2—C3 | 25.00 (15) | O2—K1—O6—C11 | 42.08 (17) |
O5—K1—O2—C3 | 119.3 (3) | C28ii—K1—O6—C11 | 109.18 (16) |
O6—K1—O2—C3 | −166.62 (15) | S1—K1—O6—C11 | −50.69 (16) |
C28ii—K1—O2—C3 | 129.81 (16) | C29ii—K1—O6—C11 | 115.96 (16) |
S1—K1—O2—C3 | −57.49 (15) | O1—K1—S1—C13 | −34.98 (10) |
C29ii—K1—O2—C3 | 106.81 (16) | O4—K1—S1—C13 | 149.02 (10) |
O1—K1—O2—C2 | −25.07 (14) | O3—K1—S1—C13 | −155.31 (10) |
O4—K1—O2—C2 | 167.97 (14) | O5—K1—S1—C13 | 85.56 (10) |
O3—K1—O2—C2 | 148.38 (15) | O6—K1—S1—C13 | 21.25 (10) |
O5—K1—O2—C2 | −117.3 (3) | O2—K1—S1—C13 | −95.14 (10) |
O6—K1—O2—C2 | −43.24 (15) | C28ii—K1—S1—C13 | −72.87 (18) |
C28ii—K1—O2—C2 | −106.81 (15) | C29ii—K1—S1—C13 | −129.08 (13) |
Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) −x+2, y−1/2, −z+1/2. |
Experimental details
(LT) | (RT) | |
Crystal data | ||
Chemical formula | [K(C19H15BNS)(C12H24O6)] | C31H39BKNO6S |
Mr | 603.6 | 603.6 |
Crystal system, space group | Orthorhombic, P212121 | Orthorhombic, P212121 |
Temperature (K) | 100 | 293 |
a, b, c (Å) | 11.034 (4), 11.582 (9), 24.149 (7) | 11.0652 (15), 11.7696 (19), 24.424 (4) |
V (Å3) | 3086 (3) | 3180.8 (8) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.28 | 0.28 |
Crystal size (mm) | 0.53 × 0.33 × 0.22 | 0.53 × 0.33 × 0.22 |
Data collection | ||
Diffractometer | Oxford Diffraction Xcalibur2 CCD | Enraf Nonius CAD4 |
Absorption correction | Numerical CrysAlis RED, Oxford Diffraction Ltd., Version 1.170.32 (release 06/06/2003 CrysAlis170 VC++). Analytical numeric absorption correction using a multifaceted crystal model. | – |
Tmin, Tmax | 0.810, 0.900 | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28274, 9621, 8301 | 13000, 5586, 4976 |
Rint | 0.048 | 0.027 |
(sin θ/λ)max (Å−1) | 0.739 | 0.594 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.095, 1.08 | 0.032, 0.094, 1.07 |
No. of reflections | 9621 | 5586 |
No. of parameters | 370 | 370 |
No. of restraints | 0 | 33 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.48, −0.40 | 0.28, −0.27 |
Absolute structure | Flack (1983) | Flack (1983); 2428 Friedel pairs. |
Absolute structure parameter | 0.08 (3) | 0.01 (4) |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), CAD-4 Software (Enraf–Nonius, ), CrysAlis RED, (Oxford Diffraction, 2003), CAD-4 Software, PROFIT (Streltsov & Zavodnik, 1989), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), WinGX WinGX (Farrugia, 1999) and ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and ORTEP-3 for Windows (Farrugia, 1997), WinGX.
C20—B1 | 1.641 (3) | K1—O3 | 2.7911 (16) |
C26—B1 | 1.632 (3) | K1—O5 | 2.7966 (15) |
C13—N1 | 1.154 (2) | K1—O6 | 2.8312 (16) |
C13—S1 | 1.6282 (19) | K1—O2 | 2.8651 (15) |
C14—B1 | 1.634 (3) | K1—C28i | 3.099 (3) |
B1—N1 | 1.567 (3) | K1—S1 | 3.2617 (17) |
K1—O4 | 2.7666 (15) | K1—C29i | 3.310 (3) |
K1—O1 | 2.7687 (15) | ||
C29—C28—K1ii | 86.39 (11) | O5—K1—C28i | 88.98 (5) |
C27—C28—K1ii | 113.15 (12) | O6—K1—C28i | 70.82 (5) |
C30—C29—K1ii | 120.82 (13) | O2—K1—C28i | 78.62 (5) |
C28—C29—K1ii | 69.12 (11) | O4—K1—S1 | 104.68 (4) |
N1—C13—S1 | 179.7 (2) | O1—K1—S1 | 87.20 (5) |
N1—B1—C26 | 106.98 (14) | O3—K1—S1 | 78.98 (3) |
N1—B1—C14 | 106.96 (14) | O5—K1—S1 | 110.46 (4) |
N1—B1—C20 | 106.98 (14) | O6—K1—S1 | 111.48 (3) |
O4—K1—O1 | 167.35 (4) | O2—K1—S1 | 82.16 (5) |
O4—K1—O3 | 60.13 (4) | C28i—K1—S1 | 159.10 (4) |
O4—K1—O5 | 60.97 (5) | O4—K1—C29i | 73.73 (5) |
O1—K1—O6 | 59.16 (4) | O1—K1—C29i | 93.83 (6) |
O3—K1—O6 | 168.84 (4) | O3—K1—C29i | 74.51 (5) |
O5—K1—O6 | 60.37 (4) | O5—K1—C29i | 95.08 (5) |
O1—K1—O2 | 60.31 (4) | O6—K1—C29i | 94.39 (5) |
O3—K1—O2 | 59.52 (4) | O2—K1—C29i | 72.59 (5) |
O5—K1—O2 | 167.36 (4) | C28i—K1—C29i | 24.49 (5) |
O4—K1—C28i | 91.23 (5) | S1—K1—C29i | 150.06 (4) |
O1—K1—C28i | 76.21 (5) | C13—N1—B1 | 174.41 (18) |
O3—K1—C28i | 98.01 (5) | C13—S1—K1 | 94.98 (7) |
O4—K1—S1—C13 | 148.19 (7) | O6—K1—S1—C13 | 18.99 (8) |
O1—K1—S1—C13 | −36.20 (7) | O2—K1—S1—C13 | −96.60 (8) |
O3—K1—S1—C13 | −156.95 (7) | C28i—K1—S1—C13 | −73.37 (13) |
O5—K1—S1—C13 | 84.14 (8) | C29i—K1—S1—C13 | −129.01 (10) |
Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) −x+2, y+1/2, −z+1/2. |
C20—B1 | 1.638 (3) | K1—O4 | 2.7651 (17) |
C26—B1 | 1.627 (3) | K1—O3 | 2.7784 (16) |
C28—K1i | 3.174 (2) | K1—O5 | 2.8010 (17) |
C29—K1i | 3.394 (3) | K1—O6 | 2.8156 (17) |
C13—N1 | 1.150 (3) | K1—O2 | 2.8602 (17) |
C13—S1 | 1.617 (2) | K1—C28ii | 3.174 (2) |
C14—B1 | 1.626 (3) | K1—S1 | 3.3064 (10) |
B1—N1 | 1.568 (3) | K1—C29ii | 3.394 (3) |
K1—O1 | 2.7604 (16) | ||
C29—C28—K1i | 87.92 (14) | O5—K1—C28ii | 89.47 (5) |
C27—C28—K1i | 112.40 (14) | O6—K1—C28ii | 72.48 (6) |
C28—C29—K1i | 69.16 (14) | O2—K1—C28ii | 78.82 (5) |
C30—C29—K1i | 121.56 (16) | O1—K1—S1 | 87.53 (4) |
N1—C13—S1 | 179.3 (2) | O4—K1—S1 | 103.74 (4) |
N1—B1—C14 | 106.59 (17) | O3—K1—S1 | 80.20 (4) |
N1—B1—C26 | 107.02 (17) | O5—K1—S1 | 108.49 (4) |
N1—B1—C20 | 107.22 (17) | O6—K1—S1 | 110.02 (4) |
O1—K1—O4 | 168.06 (5) | O2—K1—S1 | 83.39 (4) |
O4—K1—O3 | 60.04 (5) | C28ii—K1—S1 | 160.79 (5) |
O4—K1—O5 | 60.86 (5) | O1—K1—C29ii | 94.09 (6) |
O1—K1—O6 | 59.53 (5) | O4—K1—C29ii | 74.11 (6) |
O3—K1—O6 | 169.26 (5) | O3—K1—C29ii | 74.90 (6) |
O5—K1—O6 | 60.34 (5) | O5—K1—C29ii | 94.72 (6) |
O1—K1—O2 | 60.09 (5) | O6—K1—C29ii | 94.40 (6) |
O3—K1—O2 | 59.57 (5) | O2—K1—C29ii | 73.65 (5) |
O5—K1—O2 | 168.10 (5) | C28ii—K1—C29ii | 22.92 (6) |
O1—K1—C28ii | 77.36 (6) | S1—K1—C29ii | 152.28 (5) |
O4—K1—C28ii | 90.79 (6) | C13—N1—B1 | 175.3 (2) |
O3—K1—C28ii | 96.78 (6) | C13—S1—K1 | 96.95 (9) |
O1—K1—S1—C13 | −34.98 (10) | O6—K1—S1—C13 | 21.25 (10) |
O4—K1—S1—C13 | 149.02 (10) | O2—K1—S1—C13 | −95.14 (10) |
O3—K1—S1—C13 | −155.31 (10) | C28ii—K1—S1—C13 | −72.87 (18) |
O5—K1—S1—C13 | 85.56 (10) | C29ii—K1—S1—C13 | −129.08 (13) |
Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) −x+2, y−1/2, −z+1/2. |
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The thiocyanate ion is a well known ambidentate ligand that can coordinate to metal ions through the N atom (Sudbrake & Vahrenkamp, 2001) or the S atom (Uttecht & Preetz, 2001; Nelson et al., 1982). This property also favors the formation of dimeric and polymeric structures (Rudolph & Hartl, 1997; Zhang et al., 1997) in which the SCN- ion bridges identical or inequivalent metal ions to give homo- (M—S—C≡N—M) and heterobimetallic (M—S—C≡N—M') systems (Labahn et al., 1999; Harrowfield et al., 1996). Since N is a harder ligand donor than S (Pearson's classification of hard and soft bases), it is reasonable to assume that a soft metal ion, e.g. a 5 d or sixth-row main-group metal in a low oxidation state, would favor coordination to thiocyanate via the S atom (Drew et al., 1978). In contrast, hard metal ions would be expected to prefer coordination to the harder N donor and thus favor the formation of N-bound isothiocyanate complexes (Pohl et al., 1987). While these assumptions appear to be correct for many complexes, metal ions with an intermediate hard/soft character are clearly faced with two options as far as coordination to SCN- is concerned, with both N– and S-coordination to the same metal ion being found in several interesting cases (Nelson et al., 1982; Zhu et al., 2001). The fundamental question, therefore, is whether it is possible to control the manner in which thiocyanate binds to metal ions that are moderately soft.
We have recently begun an investigation of the structures and coordination chemistry of thiocyanate complexes of five- and six-coordinate FeIII and CoIII porphyrins in an effort to understand the factors that govern linkage isomerism and linear versus bent coordination of the SCN- ion in these systems (Pearson, 2002). During the course of this work, we realised that one way to control the delivery of the SCN- ion to the metal binding site is to tie up one of the donor atoms using the guiding principles of hard/soft acid/base (HSAB) theory, namely that the N atom of the SCN- ion is hard and may therefore be captured by a hard Lewis acid prior to delivery to the target metal ion (CoIII in the case of our work on porphyrins). In this paper, we show that triphenylborane (BPh3) is an easily handled Lewis acid that is well suited (if sterically bulky) to a role as an N-atom blocking group for the SCN- ion.
Selected structural parameters for (I) at 100 (1) and 293 (2) K are given in Tables 1 and 2, respectively. The following discussion pertains to the low-temperature data unless otherwise indicated. The ambidenticity of the SCN- ion is confirmed in Fig. 1(a), which clearly shows that the anion is axially coordinated to the K+ ion within the crown through its S atom and to the B atom of BPh3 through its N atom. The S1—K1 axial coordination interaction is characterized by a relatively long bond of 3.2617 (17) Å. However, since this is some 1.3 Å shorter than the sum of the van der Waals radii of the two bonded elements (4.55 Å), it is clearly a formal coordination interaction. The S1—K1 distance observed for (I) compares favorably with that reported for the YbIII derivative catena[bis(µ2-thiocyanato-N,S)-(18-crown-6)-potassium-bis(η5 -pentamethylcyclopentadienyl)ytterbium(III)] [3.226 (2) Å; Labahn et al., 1999]. The N1—B1 bond length, on the other hand, is 1.567 (3) Å and this is evidently a more regular dative covalent bond, particularly if we consider the mean B—C bond distance, which is 1.636 (5) Å. The K—O coordination distances average to 2.803 (38) Å; the large s.u. of the mean arises from the broad range [2.7666 (15)–2.8651 (15) Å; Table 1). The average cis-O—K—O and trans-O—K—O bond angles are 60.1 (6) and 167.9 (9)°, respectively. The marked deviation of the latter angle from 180° reflects the sizeable out-of-plane displacement of the K+ ion towards the axial S atom (see below).
The 18-crown-6 macrocycle has a conformation not unlike the teeth of a cylindrical saw, with the ring atoms alternately displaced above and below the mean plane of the [K(18-crown-6)]+ ion (Fig. 1 b). The maximum and minimum perpendicular atomic displacements from the mean plane of the macrocycle and K+ ion are -0.3810 (19) (C8) and 0.1352 (13) Å (O1), respectively. The K+ ion is displaced towards the axial S atom by 0.2829 (6) Å and the average value of the absolute perpendicular atomic displacements from the 19-atom mean plane is a substantial 0.257 (63) Å.
Coordination of the S atom of [SCNBPh3]- to the K+ ion of [K(18-crown-6)]+ is characterized by an unexpectedly narrow K1—S1—C13 angle of 94.98 (7)°. (The K—S—C angles in two other potassium thiocyanate derivatives are ~120°; Labahn et al., 1999; Habata et al., 2000.) Furthermore, the axial K1—S1 bond is substantially tilted from the normal to the mean plane of the metallated crown ether. This tilt is clearly evident from the O—K—S angles given in Table 1, which span a broad range from 78.98 (3) (for O3—K1—S1) to 111.48 (3)° (for O6—K1—S1), and from the view of (I) shown in Fig. 1(a). The origin of this marked structural distortion can be traced to the unexpected coordination of an aryl ring C atom to the potassium ion (trans to S1) from a neighboring molecule in the unit cell. The K1—C28iii distance [symmetry code: (iii) -x, y + 1/2, -z + 1/2] is 3.099 (3) Å and is therefore considerably shorter than the K1—S1 bond, even though the K+ ion is displaced towards the S atom. Moreover, since the K1—C29iii distance is 3.310 (3) Å, the K+ ion effectively shows asymmetric η2-type coordination to a C═C bond of the neighboring aryl ring. Organometallic complexes of potassium metal or K+ that exhibit both η1– and η2-coordination are well known (Kuhl et al., 1999; Chitsaz & Neumuller, 2001; Ganesan et al., 2002); the K—C distances are typically in the range 2.9–3.5 Å. Inspection of the Cambridge Structural Database (CSD; Allen, 2002) reveals that potassium readily forms organometallic complexes with coordination numbers as high as η8 to a single ligand in the case of bicyclic aromatic species (Cloke et al., 2000) or the cyclooctatetraenyl anion (Xia et al., 1991).
The trans-S1—K1—C28iii bond angle [159.10 (4)°] deviates significantly from 180° because of the close proximity of the crown ether to which atoms C28 and C29 are bound (Fig. 2). Steric repulsion between the neighboring crown ethers evidently requires that the K1—S1 bond and [SCNBPh3]- ion tilt away from the vector perpendicular to the mean plane of the cation in order to minimize unfavorable cation–cation and cation–anion non-bonded contacts. A useful descriptor of the lateral axial ligand displacement is the dihedral angle between the mean plane of the metallated crown ether and the triad K1—S1—C13, which is 71.75 (5)°. Interestingly, the 13C NMR spectrum of (I) showed two distinct ortho- and meta-carbon signals for the BPh3 phenyl groups, strongly suggesting that the K1—C28/C29 η2-coordination interaction observed in the solid state is also maintained in solution.
Inspection of the bond distances for (I) listed in Table 1 confirms that the thiocyanate ion has a Lewis structure that is fully consistent with a single bond between the S and C atoms and a C≡N triple bond. Furthermore, the S1—C13—N1—B1 tetrad is essentially linear, with the two bond angles subtended at atoms C13 and N1 falling within 5° of 180°. The assigned resonance form for the SCN- ion in this system is confirmed by the IR stretching frequencies for (I) (2160 cm-1 for the C≡N bond and 840 cm-1 for the C—S bond), which are typical values expected for such bonds (Nakamoto, 1986). Interestingly, the C≡N bond stretching frequency is shifted by 106 cm-1 to a higher wavenumber relative to [K(16-crown-6)(SCN)] upon coordination to BPh3. This shift reflects σ-electron donation from the N atom to a Lewis acid that is incapable of π-backbonding with the unsaturated ligand. Ultimately, an increase in polarity of the C≡N bond upon formation of the N—B bond results in the observed increase in the vibrational frequency. The key question is by how much does the electronic structure of the SCN- ion change with the addition of BPh3. Before we answer this question with AM1 (Dewar et al., 1985) calculations, it is noteworthy that the opposite appears to be true for the C—S bond, since the formation of complex (I) results in a small (7 cm-1) shift to lower frequency for the ν(CS) mode.
AM1 is parameterized for all of the elements present in (I) except K. Since our main objective in this work was to capture the N atom of the SCN- ion by coordination to boron, we have elected to focus on what effect B—N bond formation has on the electronic structure of the thiocyanate ion. The in vacuo AM1-calculated Mulliken charge distribution for [SCNBPh3]- is shown in Fig. 3(a), and that for the SCN- ion is given in Fig. 3(b). As implied by the change in the experimental vibrational frequency of the C≡N bond, the calculated charge distribution for the [SCNBPh3]- ion is consistent with marked polarization of the electron density by the B atom. Specifically, the partial negative charge on the N atom drops to 67% of its value in the free SCN- ion upon coordination to B. The fractional charge on the S atom decreases to ~54° of its value in SCN-. However, both of these changes are dwarfed by the drop in the partial negative charge for the central C atom from -0.161 e to -0.028 e (i.e. to 17° of its value in the free SCN- ion). More important is the fact that the S—C and C≡N bonds become more polar when the SCN- ion binds to BPh3. For example, the partial charge difference increases from 0.161 e to 0.188 e in going from SCN- to [SCNBPh3]- for the C≡N bond. In principle, stronger electrostatic attraction between the bonded atoms should increase the vibrational frequencies for the bonds constituting the SCN- ion.
It transpires that some useful information can be gleaned from the in vacuo AM1-calculated structures of the SCN- and [SCNBPh3]- ions. First, the calculated S—C (1.53 Å), C—N (1.18 Å), and N—B (1.53 Å) bond lengths of [SCNBPh3]- compare favorably with those determined experimentally for (I) (Table 1), even though the [K(18-crown-6)]+ ion was not included in the calculations. Secondly, the calculated S—C and C—N bond distances for the free SCN- ion (1.57 and 1.18 Å, respectively) reveal that coordination to BPh3 slightly increases the bond order, particularly of the C—S bond. The calculated vibrational frequencies for [SCNBPh3]- are thus higher [ν(C≡N) = 2385 cm-1, ν(C—S) = 855 cm-1] than for SCN- [ν(C≡N) = 2372 cm-1, ν(C—S) = 801 cm-1]. The calculated frequency change for the C≡N bond is smaller than that observed experimentally, whereas that for the C—S bond is larger and in the opposite direction. We surmise that these discrepancies probably reflect omission of the [K(18-crown-6)]+ ion from the simulations (particularly the S—K+ coordination interaction) and the relatively low level of theory inherent in the AM1 model. [We are currently running density functional theory (DFT) simulations on the present SCN- system, as well as thiocyanate and isothiocyanate complexes of a range of metalloporphyrins, in order to further elucidate the electronic structures of the SCN- ion in these species.]
The unit cell of (I) comprises four molecules (Fig. 4). As noted above, the somewhat unexpected coordination interaction between each K+ ion and the C═C bond of a neighboring BPh3 moiety leads to the formation of a helical polymer with an axis running parallel to the b axis of the unit cell, i.e. parallel to the vector joining adjacent potassium ions in the lattice. The coordination polymer may be formulated very simply by designation of its repeat unit, viz. {[K(18-crown-6)][SCNBPh3]}n. The significance of the chiral space group becomes more apparent upon inspection of the supramolecular structure of (I). Specifically, the polymer backbone, which includes the K+ ions and the ligand donor atoms S and C, is seen to spiral in a cork-screw fashion from left to right in a counterclockwise direction. Although we did not experimentally determine the absolute configuration of the crystal specimen used for the X-ray diffraction study, the left-handed helicity of the polymer chain is correct according to the Flack absolute structure parameter (Flack, 1983). (The bulk material is, of course, racemic.) Finally, it is noteworthy that other coordination polymers with bridging thiocyanate ions also crystallize in the chiral space group P212121 (Hehl & Thiele, 2000). A second, somewhat earlier, example is the copper(I) coordination polymer catena[(µ2-thiocyanato)-bis(quinoline)-copper(I)] (Healy et al., 1984).