organic compounds
Benzyltris[2-(dibenzylamino)ethyl]ammonium iodide
aDepartment of Chemistry, 1253 University of Oregon, Eugene, Oregon 97403-1253, USA, and bCAMCOR, University of Oregon, 1443 E. 13th Avenue, Eugene, Oregon 97403, USA
*Correspondence e-mail: dtyler@uoregon.edu
In the title quaternary ammonium salt, C55H61N4+·I−, all three N,N-dibenzylethanamine, –(CH2)2N(CH2C6H5)2, groups have different conformations. The N—C—C—N torsion angles are significantly different [89.86 (13), 162.61 (10) and 175.70 (10)°] and the dihedral angles between the phenyl rings in these groups are different as well [58.21 (4), 43.73 (4) and 76.72 (5)°]. In the crystal, the I− anions fill empty spaces between the bulky cations. The cations and anions are linked by weak C—H⋯I interactions, forming a chain along [110].
CCDC reference: 972778
Related literature
For related ligand structures, see: Farrell et al. (2003). For the application of similar ligands coordinating to copper in the catalysis of atom-transfer or click reactions, see: Barré et al. (2004); Candelon et al. (2008); Liang et al. (2011); Brady & Tyler (2012).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2008); cell SAINT (Bruker, 2000); 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
CCDC reference: 972778
https://doi.org/10.1107/S1600536813031607/is5322sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813031607/is5322Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536813031607/is5322Isup3.cdx
Supporting information file. DOI: https://doi.org/10.1107/S1600536813031607/is5322Isup4.cml
The title compound was prepared based on a literature procedure in which three molar equivalents of bromomethylbenzene were used (Farrell et al., 2003). As reported here, six molar equivalents of bromomethylbenzene were used. Tren (0.15 g, 1.04 mmol) was dissolved in acetonitrile (20 ml) and degassed. K2CO3 (0.55 g, 4.16 mmol) and KI (0.66 g, 4.24 mmol) were added under nitrogen. A degassed solution of bromomethylbenzene (1.08 g, 6.30 mmol) in acetonitrile (20 ml) was cannulated into the solution of deprotonated tren. The reaction solution was refluxed at 95 °C for 16 h after which time the reaction mixture was still cloudy and white. The solution was cooled to 0 °C in an ice bath and the solvent was removed in vacuo. The resulting white powder was dissolved in dichloromethane and washed with water, Na2S2O3, and water again. The solvent was removed in vacuo to yield a yellow oil. The oil was dissolved in ethyl acetate (30 ml) and heptane (15 ml) and slowly heated. Upon heating, a white powder precipitated. Based on the 1H NMR spectrum and the melting point (found: 31–125 °C, reported 50–53 °C) the product is not pure. X-ray quality crystals were prepared by slow evaporation from an ethanol solution.
H atoms were positioned geometrically (C—H = 0.95 or 0.99 Å) and refined in a rigid group model, with Uiso(H) = 1.2Ueq(C).
Work in our laboratory has focused on the preparation of nonlinear polymers containing metal-metal bonds. Most recently, synthetic methods using the Huisgen 1,3-dipolar η5-C5H4(CH2)3N3)Mo(CO)3]2, have been used. It was concluded that 1,3,5-triethynylbenzene could not be coupled to azide functionalized molecules under click reaction conditions. 1,3,5-Triethynylbenzene reacted with Cp*Ru(COD)Cl instead of clicking, and Cu(IMes)Cl was too sterically bulky to catalyze three cycloadditions (Brady & Tyler, 2012). However, similar results demonstrated that [Cu(I)tren(C18H37)6]Br can catalyze the preparation of dendrimers by the Huisgen click reaction (Candelon et al., 2008; Barré et al., 2004). Dendritic analogues of the catalyst have also been prepared and used to synthesize second generation dendrimers with 54 terminal groups (Liang et al., 2011). These examples suggest that sterics do not effect the of [Cu(I)tren(C18H37)6]Br. This warranted the examination of [Cu(I)tren(C18H37)6]Br as a catalyst to prepare a with 1,3,5-triethynylbenzene.
click reaction between 1,3,5-triethynylbenzene and an azide-functionalized molybdenum dimer, [(The title compound (1) was prepared following literature preparations for [Cu(I)tren(C18H37)6]Br. Unfortunately, 1 did not coordinate to copper so it was not examined as a click chemistry catalyst.
For related ligand structures, see: Farrell et al. (2003). For the application of similar ligands coordinated to copper in the catalysis of atom-transfer
or click reactions, see: Barré et al. (2004); Candelon et al. (2008); Liang et al. (2011); Brady & Tyler (2012).Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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. The molecular structure of the title compound, with 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms are omitted for clarity. |
C55H61N4+·I− | Z = 2 |
Mr = 904.98 | F(000) = 944 |
Triclinic, P1 | Dx = 1.267 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.1254 (10) Å | Cell parameters from 9619 reflections |
b = 14.3871 (13) Å | θ = 2.6–36.2° |
c = 15.9525 (15) Å | µ = 0.72 mm−1 |
α = 94.491 (3)° | T = 100 K |
β = 101.972 (3)° | Prizm, colourless |
γ = 106.229 (3)° | 0.25 × 0.24 × 0.11 mm |
V = 2372.9 (4) Å3 |
Bruker APEXII CCD diffractometer | 10377 independent reflections |
Radiation source: fine-focus sealed tube | 9802 reflections with I > 2σ(I) |
Triumph mirror monochromator | Rint = 0.030 |
φ and ω scans | θmax = 27.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −14→14 |
Tmin = 0.842, Tmax = 0.926 | k = −18→16 |
53881 measured reflections | l = −20→20 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.020 | H-atom parameters constrained |
wR(F2) = 0.049 | w = 1/[σ2(Fo2) + (0.0153P)2 + 1.324P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.002 |
10377 reflections | Δρmax = 0.38 e Å−3 |
542 parameters | Δρmin = −0.42 e Å−3 |
0 restraints | Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00066 (14) |
C55H61N4+·I− | γ = 106.229 (3)° |
Mr = 904.98 | V = 2372.9 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.1254 (10) Å | Mo Kα radiation |
b = 14.3871 (13) Å | µ = 0.72 mm−1 |
c = 15.9525 (15) Å | T = 100 K |
α = 94.491 (3)° | 0.25 × 0.24 × 0.11 mm |
β = 101.972 (3)° |
Bruker APEXII CCD diffractometer | 10377 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 9802 reflections with I > 2σ(I) |
Tmin = 0.842, Tmax = 0.926 | Rint = 0.030 |
53881 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 0 restraints |
wR(F2) = 0.049 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.38 e Å−3 |
10377 reflections | Δρmin = −0.42 e Å−3 |
542 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 | ||
I1 | 0.258461 (8) | 0.304462 (6) | 0.946780 (6) | 0.01859 (3) | |
N1 | 0.65830 (9) | 0.40260 (7) | 0.14758 (6) | 0.0115 (2) | |
N2 | 0.92688 (10) | 0.57153 (8) | 0.27511 (7) | 0.0148 (2) | |
N3 | 0.47013 (10) | 0.54906 (8) | 0.24366 (7) | 0.0153 (2) | |
N4 | 0.46942 (10) | 0.17927 (8) | 0.22778 (7) | 0.0174 (2) | |
C1 | 0.79639 (11) | 0.40571 (9) | 0.18740 (8) | 0.0141 (2) | |
H1A | 0.8182 | 0.3557 | 0.1524 | 0.017* | |
H1B | 0.8006 | 0.3872 | 0.2462 | 0.017* | |
C2 | 0.89895 (12) | 0.50425 (9) | 0.19438 (8) | 0.0157 (2) | |
H2A | 0.9800 | 0.4917 | 0.1882 | 0.019* | |
H2B | 0.8708 | 0.5373 | 0.1452 | 0.019* | |
C3 | 1.01512 (12) | 0.66504 (10) | 0.26363 (9) | 0.0194 (3) | |
H3A | 0.9779 | 0.6844 | 0.2083 | 0.023* | |
H3B | 1.0982 | 0.6549 | 0.2593 | 0.023* | |
C4 | 1.04092 (13) | 0.74770 (10) | 0.33570 (9) | 0.0208 (3) | |
C5 | 0.94103 (15) | 0.76527 (11) | 0.36803 (10) | 0.0282 (3) | |
H5A | 0.8557 | 0.7224 | 0.3468 | 0.034* | |
C6 | 0.96470 (19) | 0.84485 (12) | 0.43104 (12) | 0.0383 (4) | |
H6A | 0.8959 | 0.8557 | 0.4531 | 0.046* | |
C7 | 1.08893 (19) | 0.90862 (11) | 0.46183 (11) | 0.0397 (4) | |
H7A | 1.1053 | 0.9633 | 0.5046 | 0.048* | |
C8 | 1.18838 (18) | 0.89196 (11) | 0.42988 (11) | 0.0358 (4) | |
H8A | 1.2733 | 0.9356 | 0.4505 | 0.043* | |
C9 | 1.16503 (15) | 0.81164 (11) | 0.36767 (9) | 0.0266 (3) | |
H9A | 1.2344 | 0.8003 | 0.3468 | 0.032* | |
C10 | 0.98820 (12) | 0.53424 (10) | 0.35122 (9) | 0.0178 (3) | |
H10A | 1.0436 | 0.5907 | 0.3950 | 0.021* | |
H10B | 1.0447 | 0.4983 | 0.3331 | 0.021* | |
C11 | 0.89454 (12) | 0.46742 (10) | 0.39318 (8) | 0.0166 (2) | |
C12 | 0.90450 (13) | 0.37526 (10) | 0.40752 (8) | 0.0196 (3) | |
H12A | 0.9692 | 0.3535 | 0.3891 | 0.024* | |
C13 | 0.82121 (14) | 0.31463 (11) | 0.44837 (9) | 0.0235 (3) | |
H13A | 0.8297 | 0.2522 | 0.4579 | 0.028* | |
C14 | 0.72586 (14) | 0.34508 (12) | 0.47524 (9) | 0.0255 (3) | |
H14A | 0.6684 | 0.3036 | 0.5028 | 0.031* | |
C15 | 0.71505 (14) | 0.43675 (12) | 0.46156 (9) | 0.0254 (3) | |
H15A | 0.6499 | 0.4580 | 0.4799 | 0.030* | |
C16 | 0.79869 (13) | 0.49771 (11) | 0.42131 (9) | 0.0205 (3) | |
H16A | 0.7907 | 0.5605 | 0.4128 | 0.025* | |
C17 | 0.62902 (11) | 0.48370 (9) | 0.19850 (8) | 0.0134 (2) | |
H17A | 0.6886 | 0.5471 | 0.1926 | 0.016* | |
H17B | 0.6480 | 0.4758 | 0.2605 | 0.016* | |
C18 | 0.49129 (12) | 0.48881 (9) | 0.17232 (8) | 0.0152 (2) | |
H18A | 0.4789 | 0.5185 | 0.1185 | 0.018* | |
H18B | 0.4291 | 0.4223 | 0.1618 | 0.018* | |
C19 | 0.54626 (13) | 0.65255 (10) | 0.25103 (9) | 0.0191 (3) | |
H19A | 0.5050 | 0.6821 | 0.2036 | 0.023* | |
H19B | 0.6335 | 0.6559 | 0.2438 | 0.023* | |
C20 | 0.55863 (12) | 0.71169 (10) | 0.33658 (9) | 0.0187 (3) | |
C21 | 0.57529 (13) | 0.67301 (11) | 0.41403 (9) | 0.0227 (3) | |
H21A | 0.5734 | 0.6065 | 0.4131 | 0.027* | |
C22 | 0.59459 (14) | 0.73056 (12) | 0.49277 (10) | 0.0281 (3) | |
H22A | 0.6061 | 0.7033 | 0.5451 | 0.034* | |
C23 | 0.59709 (16) | 0.82747 (12) | 0.49503 (10) | 0.0328 (4) | |
H23A | 0.6109 | 0.8669 | 0.5488 | 0.039* | |
C24 | 0.57942 (19) | 0.86637 (12) | 0.41876 (11) | 0.0377 (4) | |
H24A | 0.5801 | 0.9326 | 0.4200 | 0.045* | |
C25 | 0.56057 (16) | 0.80891 (11) | 0.33983 (10) | 0.0290 (3) | |
H25A | 0.5489 | 0.8365 | 0.2877 | 0.035* | |
C26 | 0.33205 (12) | 0.54272 (10) | 0.22862 (9) | 0.0194 (3) | |
H26A | 0.3037 | 0.5604 | 0.1707 | 0.023* | |
H26B | 0.3220 | 0.5912 | 0.2721 | 0.023* | |
C27 | 0.24552 (12) | 0.44284 (10) | 0.23376 (9) | 0.0198 (3) | |
C28 | 0.15843 (13) | 0.38517 (11) | 0.15984 (10) | 0.0251 (3) | |
H28A | 0.1569 | 0.4075 | 0.1053 | 0.030* | |
C29 | 0.07355 (15) | 0.29513 (12) | 0.16496 (12) | 0.0349 (4) | |
H29A | 0.0149 | 0.2565 | 0.1140 | 0.042* | |
C30 | 0.07459 (16) | 0.26210 (12) | 0.24384 (14) | 0.0391 (4) | |
H30A | 0.0156 | 0.2013 | 0.2476 | 0.047* | |
C31 | 0.16209 (16) | 0.31805 (13) | 0.31769 (12) | 0.0355 (4) | |
H31A | 0.1639 | 0.2949 | 0.3720 | 0.043* | |
C32 | 0.24727 (14) | 0.40774 (12) | 0.31282 (10) | 0.0263 (3) | |
H32A | 0.3071 | 0.4454 | 0.3638 | 0.032* | |
C33 | 0.57049 (11) | 0.30202 (9) | 0.15075 (8) | 0.0133 (2) | |
H33A | 0.5978 | 0.2528 | 0.1189 | 0.016* | |
H33B | 0.4818 | 0.2975 | 0.1196 | 0.016* | |
C34 | 0.56666 (13) | 0.27480 (10) | 0.24087 (8) | 0.0194 (3) | |
H34A | 0.6519 | 0.2713 | 0.2716 | 0.023* | |
H34B | 0.5429 | 0.3240 | 0.2755 | 0.023* | |
C35 | 0.34292 (14) | 0.18551 (11) | 0.23591 (10) | 0.0237 (3) | |
H35A | 0.3258 | 0.2419 | 0.2094 | 0.028* | |
H35B | 0.3427 | 0.1961 | 0.2979 | 0.028* | |
C36 | 0.23870 (13) | 0.09302 (11) | 0.19179 (11) | 0.0254 (3) | |
C37 | 0.21898 (14) | 0.06601 (11) | 0.10272 (11) | 0.0285 (3) | |
H37A | 0.2703 | 0.1069 | 0.0712 | 0.034* | |
C38 | 0.12591 (15) | −0.01933 (13) | 0.05975 (14) | 0.0415 (4) | |
H38A | 0.1143 | −0.0370 | −0.0007 | 0.050* | |
C39 | 0.04972 (16) | −0.07896 (13) | 0.10474 (18) | 0.0511 (6) | |
H39A | −0.0151 | −0.1371 | 0.0751 | 0.061* | |
C40 | 0.06773 (16) | −0.05418 (14) | 0.19217 (18) | 0.0540 (7) | |
H40A | 0.0157 | −0.0957 | 0.2229 | 0.065* | |
C41 | 0.16278 (15) | 0.03243 (13) | 0.23692 (14) | 0.0389 (4) | |
H41A | 0.1748 | 0.0492 | 0.2975 | 0.047* | |
C42 | 0.51333 (13) | 0.10956 (10) | 0.27861 (9) | 0.0211 (3) | |
H42A | 0.4379 | 0.0545 | 0.2811 | 0.025* | |
H42B | 0.5570 | 0.1422 | 0.3385 | 0.025* | |
C43 | 0.60544 (13) | 0.07035 (10) | 0.23936 (10) | 0.0218 (3) | |
C44 | 0.71526 (15) | 0.05800 (12) | 0.29130 (11) | 0.0302 (3) | |
H44A | 0.7368 | 0.0789 | 0.3520 | 0.036* | |
C45 | 0.79374 (16) | 0.01507 (14) | 0.25478 (13) | 0.0412 (4) | |
H45A | 0.8684 | 0.0067 | 0.2907 | 0.049* | |
C46 | 0.76366 (18) | −0.01528 (16) | 0.16680 (15) | 0.0492 (5) | |
H46A | 0.8160 | −0.0461 | 0.1422 | 0.059* | |
C47 | 0.65645 (19) | −0.00045 (17) | 0.11451 (14) | 0.0519 (6) | |
H47A | 0.6366 | −0.0194 | 0.0536 | 0.062* | |
C48 | 0.57798 (15) | 0.04207 (13) | 0.15092 (11) | 0.0353 (4) | |
H48A | 0.5046 | 0.0518 | 0.1147 | 0.042* | |
C49 | 0.64012 (12) | 0.41892 (9) | 0.05210 (8) | 0.0136 (2) | |
H49A | 0.5471 | 0.4068 | 0.0266 | 0.016* | |
H49B | 0.6849 | 0.4883 | 0.0498 | 0.016* | |
C50 | 0.68975 (13) | 0.35503 (10) | −0.00260 (8) | 0.0163 (2) | |
C51 | 0.81668 (14) | 0.38692 (12) | −0.01157 (9) | 0.0239 (3) | |
H51A | 0.8725 | 0.4486 | 0.0183 | 0.029* | |
C52 | 0.86189 (16) | 0.32936 (14) | −0.06375 (10) | 0.0332 (4) | |
H52A | 0.9488 | 0.3510 | −0.0684 | 0.040* | |
C53 | 0.78044 (18) | 0.24072 (14) | −0.10873 (10) | 0.0366 (4) | |
H53A | 0.8110 | 0.2017 | −0.1450 | 0.044* | |
C54 | 0.65424 (18) | 0.20851 (12) | −0.10119 (10) | 0.0320 (4) | |
H54A | 0.5986 | 0.1474 | −0.1323 | 0.038* | |
C55 | 0.60823 (14) | 0.26518 (10) | −0.04828 (9) | 0.0214 (3) | |
H55A | 0.5215 | 0.2427 | −0.0433 | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.01564 (5) | 0.01370 (5) | 0.02282 (5) | 0.00055 (3) | 0.00239 (3) | 0.00193 (3) |
N1 | 0.0111 (5) | 0.0116 (5) | 0.0110 (5) | 0.0031 (4) | 0.0018 (4) | −0.0005 (4) |
N2 | 0.0133 (5) | 0.0141 (5) | 0.0143 (5) | 0.0023 (4) | 0.0002 (4) | 0.0000 (4) |
N3 | 0.0141 (5) | 0.0160 (5) | 0.0163 (5) | 0.0059 (4) | 0.0045 (4) | −0.0015 (4) |
N4 | 0.0177 (5) | 0.0148 (5) | 0.0206 (6) | 0.0041 (4) | 0.0067 (4) | 0.0059 (4) |
C1 | 0.0107 (5) | 0.0151 (6) | 0.0152 (6) | 0.0047 (5) | 0.0003 (4) | −0.0011 (5) |
C2 | 0.0117 (5) | 0.0176 (6) | 0.0161 (6) | 0.0033 (5) | 0.0026 (5) | −0.0018 (5) |
C3 | 0.0158 (6) | 0.0185 (6) | 0.0193 (7) | −0.0002 (5) | 0.0023 (5) | 0.0010 (5) |
C4 | 0.0252 (7) | 0.0141 (6) | 0.0179 (7) | 0.0020 (5) | −0.0012 (5) | 0.0032 (5) |
C5 | 0.0298 (8) | 0.0216 (7) | 0.0297 (8) | 0.0089 (6) | 0.0006 (6) | −0.0028 (6) |
C6 | 0.0511 (10) | 0.0274 (8) | 0.0369 (9) | 0.0209 (8) | 0.0029 (8) | −0.0043 (7) |
C7 | 0.0643 (12) | 0.0164 (7) | 0.0289 (9) | 0.0120 (8) | −0.0064 (8) | −0.0041 (6) |
C8 | 0.0460 (10) | 0.0173 (7) | 0.0271 (8) | −0.0042 (7) | −0.0086 (7) | 0.0026 (6) |
C9 | 0.0294 (8) | 0.0201 (7) | 0.0211 (7) | −0.0022 (6) | −0.0016 (6) | 0.0055 (6) |
C10 | 0.0134 (6) | 0.0195 (6) | 0.0181 (6) | 0.0047 (5) | −0.0009 (5) | 0.0016 (5) |
C11 | 0.0152 (6) | 0.0206 (6) | 0.0107 (6) | 0.0046 (5) | −0.0018 (5) | −0.0016 (5) |
C12 | 0.0203 (6) | 0.0235 (7) | 0.0140 (6) | 0.0081 (5) | 0.0004 (5) | 0.0009 (5) |
C13 | 0.0275 (7) | 0.0244 (7) | 0.0145 (7) | 0.0059 (6) | −0.0015 (5) | 0.0041 (6) |
C14 | 0.0214 (7) | 0.0365 (8) | 0.0137 (7) | 0.0019 (6) | 0.0022 (5) | 0.0062 (6) |
C15 | 0.0200 (7) | 0.0407 (9) | 0.0152 (7) | 0.0105 (6) | 0.0037 (5) | −0.0009 (6) |
C16 | 0.0204 (6) | 0.0247 (7) | 0.0153 (6) | 0.0087 (6) | 0.0010 (5) | −0.0017 (5) |
C17 | 0.0135 (6) | 0.0127 (6) | 0.0132 (6) | 0.0049 (5) | 0.0018 (4) | −0.0025 (5) |
C18 | 0.0138 (6) | 0.0171 (6) | 0.0142 (6) | 0.0062 (5) | 0.0022 (5) | −0.0016 (5) |
C19 | 0.0237 (7) | 0.0165 (6) | 0.0181 (7) | 0.0065 (5) | 0.0073 (5) | 0.0003 (5) |
C20 | 0.0163 (6) | 0.0195 (6) | 0.0191 (7) | 0.0041 (5) | 0.0050 (5) | −0.0021 (5) |
C21 | 0.0222 (7) | 0.0247 (7) | 0.0218 (7) | 0.0083 (6) | 0.0056 (5) | 0.0008 (6) |
C22 | 0.0269 (7) | 0.0364 (8) | 0.0186 (7) | 0.0054 (7) | 0.0069 (6) | 0.0008 (6) |
C23 | 0.0370 (9) | 0.0298 (8) | 0.0230 (8) | −0.0024 (7) | 0.0113 (7) | −0.0110 (6) |
C24 | 0.0571 (11) | 0.0184 (7) | 0.0334 (9) | 0.0051 (7) | 0.0147 (8) | −0.0069 (7) |
C25 | 0.0434 (9) | 0.0204 (7) | 0.0217 (7) | 0.0072 (7) | 0.0089 (6) | −0.0003 (6) |
C26 | 0.0173 (6) | 0.0222 (7) | 0.0215 (7) | 0.0113 (5) | 0.0044 (5) | 0.0009 (5) |
C27 | 0.0147 (6) | 0.0250 (7) | 0.0247 (7) | 0.0119 (5) | 0.0083 (5) | 0.0019 (6) |
C28 | 0.0184 (6) | 0.0285 (7) | 0.0301 (8) | 0.0106 (6) | 0.0065 (6) | −0.0001 (6) |
C29 | 0.0198 (7) | 0.0293 (8) | 0.0523 (11) | 0.0066 (6) | 0.0066 (7) | −0.0057 (8) |
C30 | 0.0229 (8) | 0.0280 (8) | 0.0748 (14) | 0.0103 (7) | 0.0246 (8) | 0.0124 (9) |
C31 | 0.0328 (8) | 0.0428 (10) | 0.0499 (10) | 0.0236 (8) | 0.0281 (8) | 0.0233 (8) |
C32 | 0.0241 (7) | 0.0355 (8) | 0.0269 (8) | 0.0168 (6) | 0.0111 (6) | 0.0060 (6) |
C33 | 0.0136 (5) | 0.0108 (5) | 0.0134 (6) | 0.0016 (5) | 0.0022 (4) | −0.0003 (5) |
C34 | 0.0236 (7) | 0.0166 (6) | 0.0137 (6) | 0.0003 (5) | 0.0030 (5) | 0.0017 (5) |
C35 | 0.0260 (7) | 0.0250 (7) | 0.0274 (8) | 0.0129 (6) | 0.0136 (6) | 0.0084 (6) |
C36 | 0.0172 (6) | 0.0232 (7) | 0.0434 (9) | 0.0111 (6) | 0.0128 (6) | 0.0171 (7) |
C37 | 0.0188 (7) | 0.0237 (7) | 0.0419 (9) | 0.0060 (6) | 0.0042 (6) | 0.0091 (7) |
C38 | 0.0212 (8) | 0.0293 (8) | 0.0658 (13) | 0.0067 (7) | −0.0052 (8) | 0.0046 (8) |
C39 | 0.0175 (8) | 0.0269 (9) | 0.1046 (19) | 0.0057 (7) | 0.0025 (9) | 0.0204 (10) |
C40 | 0.0201 (8) | 0.0378 (10) | 0.123 (2) | 0.0169 (8) | 0.0307 (10) | 0.0538 (13) |
C41 | 0.0259 (8) | 0.0417 (10) | 0.0671 (12) | 0.0213 (7) | 0.0251 (8) | 0.0364 (9) |
C42 | 0.0221 (7) | 0.0203 (7) | 0.0243 (7) | 0.0073 (5) | 0.0088 (5) | 0.0103 (6) |
C43 | 0.0180 (6) | 0.0153 (6) | 0.0315 (8) | 0.0033 (5) | 0.0067 (6) | 0.0038 (6) |
C44 | 0.0262 (7) | 0.0305 (8) | 0.0349 (9) | 0.0103 (6) | 0.0051 (6) | 0.0100 (7) |
C45 | 0.0253 (8) | 0.0449 (10) | 0.0573 (12) | 0.0186 (8) | 0.0064 (8) | 0.0101 (9) |
C46 | 0.0337 (9) | 0.0540 (12) | 0.0659 (14) | 0.0257 (9) | 0.0133 (9) | −0.0060 (10) |
C47 | 0.0395 (10) | 0.0713 (14) | 0.0428 (11) | 0.0289 (10) | 0.0007 (8) | −0.0234 (10) |
C48 | 0.0241 (7) | 0.0432 (10) | 0.0357 (9) | 0.0161 (7) | −0.0013 (7) | −0.0106 (8) |
C49 | 0.0149 (6) | 0.0144 (6) | 0.0114 (6) | 0.0047 (5) | 0.0025 (4) | 0.0020 (5) |
C50 | 0.0216 (6) | 0.0198 (6) | 0.0111 (6) | 0.0103 (5) | 0.0055 (5) | 0.0039 (5) |
C51 | 0.0230 (7) | 0.0348 (8) | 0.0175 (7) | 0.0118 (6) | 0.0077 (5) | 0.0065 (6) |
C52 | 0.0338 (8) | 0.0565 (11) | 0.0241 (8) | 0.0286 (8) | 0.0158 (7) | 0.0131 (8) |
C53 | 0.0596 (11) | 0.0479 (10) | 0.0248 (8) | 0.0417 (9) | 0.0216 (8) | 0.0110 (7) |
C54 | 0.0571 (11) | 0.0240 (8) | 0.0200 (7) | 0.0199 (8) | 0.0104 (7) | 0.0010 (6) |
C55 | 0.0309 (7) | 0.0195 (7) | 0.0158 (7) | 0.0101 (6) | 0.0068 (5) | 0.0025 (5) |
N1—C33 | 1.5142 (15) | C24—H24A | 0.9500 |
N1—C17 | 1.5169 (15) | C25—H25A | 0.9500 |
N1—C1 | 1.5225 (14) | C26—C27 | 1.5088 (19) |
N1—C49 | 1.5397 (15) | C26—H26A | 0.9900 |
N2—C2 | 1.4706 (16) | C26—H26B | 0.9900 |
N2—C3 | 1.4772 (16) | C27—C32 | 1.393 (2) |
N2—C10 | 1.4800 (16) | C27—C28 | 1.393 (2) |
N3—C18 | 1.4740 (16) | C28—C29 | 1.393 (2) |
N3—C19 | 1.4745 (17) | C28—H28A | 0.9500 |
N3—C26 | 1.4802 (16) | C29—C30 | 1.378 (3) |
N4—C34 | 1.4605 (17) | C29—H29A | 0.9500 |
N4—C42 | 1.4626 (16) | C30—C31 | 1.386 (3) |
N4—C35 | 1.4663 (17) | C30—H30A | 0.9500 |
C1—C2 | 1.5305 (17) | C31—C32 | 1.390 (2) |
C1—H1A | 0.9900 | C31—H31A | 0.9500 |
C1—H1B | 0.9900 | C32—H32A | 0.9500 |
C2—H2A | 0.9900 | C33—C34 | 1.5252 (17) |
C2—H2B | 0.9900 | C33—H33A | 0.9900 |
C3—C4 | 1.5088 (19) | C33—H33B | 0.9900 |
C3—H3A | 0.9900 | C34—H34A | 0.9900 |
C3—H3B | 0.9900 | C34—H34B | 0.9900 |
C4—C9 | 1.392 (2) | C35—C36 | 1.504 (2) |
C4—C5 | 1.393 (2) | C35—H35A | 0.9900 |
C5—C6 | 1.390 (2) | C35—H35B | 0.9900 |
C5—H5A | 0.9500 | C36—C41 | 1.390 (2) |
C6—C7 | 1.390 (3) | C36—C37 | 1.398 (2) |
C6—H6A | 0.9500 | C37—C38 | 1.383 (2) |
C7—C8 | 1.380 (3) | C37—H37A | 0.9500 |
C7—H7A | 0.9500 | C38—C39 | 1.383 (3) |
C8—C9 | 1.390 (2) | C38—H38A | 0.9500 |
C8—H8A | 0.9500 | C39—C40 | 1.371 (3) |
C9—H9A | 0.9500 | C39—H39A | 0.9500 |
C10—C11 | 1.5127 (18) | C40—C41 | 1.411 (3) |
C10—H10A | 0.9900 | C40—H40A | 0.9500 |
C10—H10B | 0.9900 | C41—H41A | 0.9500 |
C11—C12 | 1.3935 (19) | C42—C43 | 1.5147 (19) |
C11—C16 | 1.3985 (18) | C42—H42A | 0.9900 |
C12—C13 | 1.390 (2) | C42—H42B | 0.9900 |
C12—H12A | 0.9500 | C43—C48 | 1.382 (2) |
C13—C14 | 1.386 (2) | C43—C44 | 1.391 (2) |
C13—H13A | 0.9500 | C44—C45 | 1.393 (2) |
C14—C15 | 1.387 (2) | C44—H44A | 0.9500 |
C14—H14A | 0.9500 | C45—C46 | 1.378 (3) |
C15—C16 | 1.388 (2) | C45—H45A | 0.9500 |
C15—H15A | 0.9500 | C46—C47 | 1.386 (3) |
C16—H16A | 0.9500 | C46—H46A | 0.9500 |
C17—C18 | 1.5265 (16) | C47—C48 | 1.388 (2) |
C17—H17A | 0.9900 | C47—H47A | 0.9500 |
C17—H17B | 0.9900 | C48—H48A | 0.9500 |
C18—H18A | 0.9900 | C49—C50 | 1.5064 (17) |
C18—H18B | 0.9900 | C49—H49A | 0.9900 |
C19—C20 | 1.5101 (19) | C49—H49B | 0.9900 |
C19—H19A | 0.9900 | C50—C55 | 1.3955 (19) |
C19—H19B | 0.9900 | C50—C51 | 1.3990 (19) |
C20—C25 | 1.390 (2) | C51—C52 | 1.389 (2) |
C20—C21 | 1.3931 (19) | C51—H51A | 0.9500 |
C21—C22 | 1.391 (2) | C52—C53 | 1.380 (3) |
C21—H21A | 0.9500 | C52—H52A | 0.9500 |
C22—C23 | 1.384 (2) | C53—C54 | 1.384 (3) |
C22—H22A | 0.9500 | C53—H53A | 0.9500 |
C23—C24 | 1.379 (2) | C54—C55 | 1.394 (2) |
C23—H23A | 0.9500 | C54—H54A | 0.9500 |
C24—C25 | 1.394 (2) | C55—H55A | 0.9500 |
C33—N1—C17 | 112.71 (9) | C24—C25—H25A | 119.6 |
C33—N1—C1 | 108.08 (9) | N3—C26—C27 | 113.79 (10) |
C17—N1—C1 | 107.80 (9) | N3—C26—H26A | 108.8 |
C33—N1—C49 | 107.91 (9) | C27—C26—H26A | 108.8 |
C17—N1—C49 | 108.85 (9) | N3—C26—H26B | 108.8 |
C1—N1—C49 | 111.53 (9) | C27—C26—H26B | 108.8 |
C2—N2—C3 | 106.50 (10) | H26A—C26—H26B | 107.7 |
C2—N2—C10 | 112.13 (10) | C32—C27—C28 | 118.49 (14) |
C3—N2—C10 | 109.80 (10) | C32—C27—C26 | 120.88 (13) |
C18—N3—C19 | 111.12 (10) | C28—C27—C26 | 120.58 (13) |
C18—N3—C26 | 110.13 (10) | C29—C28—C27 | 120.82 (15) |
C19—N3—C26 | 108.59 (10) | C29—C28—H28A | 119.6 |
C34—N4—C42 | 113.12 (11) | C27—C28—H28A | 119.6 |
C34—N4—C35 | 113.16 (11) | C30—C29—C28 | 120.11 (16) |
C42—N4—C35 | 113.38 (10) | C30—C29—H29A | 119.9 |
N1—C1—C2 | 115.62 (10) | C28—C29—H29A | 119.9 |
N1—C1—H1A | 108.4 | C29—C30—C31 | 119.66 (15) |
C2—C1—H1A | 108.4 | C29—C30—H30A | 120.2 |
N1—C1—H1B | 108.4 | C31—C30—H30A | 120.2 |
C2—C1—H1B | 108.4 | C30—C31—C32 | 120.42 (16) |
H1A—C1—H1B | 107.4 | C30—C31—H31A | 119.8 |
N2—C2—C1 | 115.67 (10) | C32—C31—H31A | 119.8 |
N2—C2—H2A | 108.4 | C31—C32—C27 | 120.49 (15) |
C1—C2—H2A | 108.4 | C31—C32—H32A | 119.8 |
N2—C2—H2B | 108.4 | C27—C32—H32A | 119.8 |
C1—C2—H2B | 108.4 | N1—C33—C34 | 116.02 (10) |
H2A—C2—H2B | 107.4 | N1—C33—H33A | 108.3 |
N2—C3—C4 | 114.09 (11) | C34—C33—H33A | 108.3 |
N2—C3—H3A | 108.7 | N1—C33—H33B | 108.3 |
C4—C3—H3A | 108.7 | C34—C33—H33B | 108.3 |
N2—C3—H3B | 108.7 | H33A—C33—H33B | 107.4 |
C4—C3—H3B | 108.7 | N4—C34—C33 | 106.11 (10) |
H3A—C3—H3B | 107.6 | N4—C34—H34A | 110.5 |
C9—C4—C5 | 118.61 (14) | C33—C34—H34A | 110.5 |
C9—C4—C3 | 120.12 (13) | N4—C34—H34B | 110.5 |
C5—C4—C3 | 121.16 (12) | C33—C34—H34B | 110.5 |
C6—C5—C4 | 120.75 (15) | H34A—C34—H34B | 108.7 |
C6—C5—H5A | 119.6 | N4—C35—C36 | 110.46 (11) |
C4—C5—H5A | 119.6 | N4—C35—H35A | 109.6 |
C5—C6—C7 | 120.03 (17) | C36—C35—H35A | 109.6 |
C5—C6—H6A | 120.0 | N4—C35—H35B | 109.6 |
C7—C6—H6A | 120.0 | C36—C35—H35B | 109.6 |
C8—C7—C6 | 119.59 (15) | H35A—C35—H35B | 108.1 |
C8—C7—H7A | 120.2 | C41—C36—C37 | 118.79 (16) |
C6—C7—H7A | 120.2 | C41—C36—C35 | 122.16 (16) |
C7—C8—C9 | 120.39 (16) | C37—C36—C35 | 119.04 (13) |
C7—C8—H8A | 119.8 | C38—C37—C36 | 121.03 (16) |
C9—C8—H8A | 119.8 | C38—C37—H37A | 119.5 |
C8—C9—C4 | 120.62 (16) | C36—C37—H37A | 119.5 |
C8—C9—H9A | 119.7 | C37—C38—C39 | 120.0 (2) |
C4—C9—H9A | 119.7 | C37—C38—H38A | 120.0 |
N2—C10—C11 | 114.59 (10) | C39—C38—H38A | 120.0 |
N2—C10—H10A | 108.6 | C40—C39—C38 | 119.98 (18) |
C11—C10—H10A | 108.6 | C40—C39—H39A | 120.0 |
N2—C10—H10B | 108.6 | C38—C39—H39A | 120.0 |
C11—C10—H10B | 108.6 | C39—C40—C41 | 120.61 (17) |
H10A—C10—H10B | 107.6 | C39—C40—H40A | 119.7 |
C12—C11—C16 | 118.26 (13) | C41—C40—H40A | 119.7 |
C12—C11—C10 | 120.72 (12) | C36—C41—C40 | 119.58 (19) |
C16—C11—C10 | 120.98 (12) | C36—C41—H41A | 120.2 |
C13—C12—C11 | 121.05 (13) | C40—C41—H41A | 120.2 |
C13—C12—H12A | 119.5 | N4—C42—C43 | 111.18 (11) |
C11—C12—H12A | 119.5 | N4—C42—H42A | 109.4 |
C14—C13—C12 | 120.16 (13) | C43—C42—H42A | 109.4 |
C14—C13—H13A | 119.9 | N4—C42—H42B | 109.4 |
C12—C13—H13A | 119.9 | C43—C42—H42B | 109.4 |
C13—C14—C15 | 119.39 (13) | H42A—C42—H42B | 108.0 |
C13—C14—H14A | 120.3 | C48—C43—C44 | 118.90 (14) |
C15—C14—H14A | 120.3 | C48—C43—C42 | 119.97 (13) |
C16—C15—C14 | 120.55 (13) | C44—C43—C42 | 121.06 (14) |
C16—C15—H15A | 119.7 | C43—C44—C45 | 120.30 (16) |
C14—C15—H15A | 119.7 | C43—C44—H44A | 119.8 |
C15—C16—C11 | 120.58 (13) | C45—C44—H44A | 119.8 |
C15—C16—H16A | 119.7 | C46—C45—C44 | 120.35 (16) |
C11—C16—H16A | 119.7 | C46—C45—H45A | 119.8 |
N1—C17—C18 | 116.01 (10) | C44—C45—H45A | 119.8 |
N1—C17—H17A | 108.3 | C45—C46—C47 | 119.50 (16) |
C18—C17—H17A | 108.3 | C45—C46—H46A | 120.3 |
N1—C17—H17B | 108.3 | C47—C46—H46A | 120.3 |
C18—C17—H17B | 108.3 | C46—C47—C48 | 120.14 (18) |
H17A—C17—H17B | 107.4 | C46—C47—H47A | 119.9 |
N3—C18—C17 | 107.82 (10) | C48—C47—H47A | 119.9 |
N3—C18—H18A | 110.1 | C43—C48—C47 | 120.75 (15) |
C17—C18—H18A | 110.1 | C43—C48—H48A | 119.6 |
N3—C18—H18B | 110.1 | C47—C48—H48A | 119.6 |
C17—C18—H18B | 110.1 | C50—C49—N1 | 114.38 (9) |
H18A—C18—H18B | 108.5 | C50—C49—H49A | 108.7 |
N3—C19—C20 | 113.15 (11) | N1—C49—H49A | 108.7 |
N3—C19—H19A | 108.9 | C50—C49—H49B | 108.7 |
C20—C19—H19A | 108.9 | N1—C49—H49B | 108.7 |
N3—C19—H19B | 108.9 | H49A—C49—H49B | 107.6 |
C20—C19—H19B | 108.9 | C55—C50—C51 | 118.94 (13) |
H19A—C19—H19B | 107.8 | C55—C50—C49 | 120.55 (12) |
C25—C20—C21 | 118.38 (13) | C51—C50—C49 | 120.45 (12) |
C25—C20—C19 | 119.85 (12) | C52—C51—C50 | 120.67 (15) |
C21—C20—C19 | 121.68 (12) | C52—C51—H51A | 119.7 |
C22—C21—C20 | 120.81 (14) | C50—C51—H51A | 119.7 |
C22—C21—H21A | 119.6 | C53—C52—C51 | 119.91 (15) |
C20—C21—H21A | 119.6 | C53—C52—H52A | 120.0 |
C23—C22—C21 | 120.15 (14) | C51—C52—H52A | 120.0 |
C23—C22—H22A | 119.9 | C52—C53—C54 | 120.14 (14) |
C21—C22—H22A | 119.9 | C52—C53—H53A | 119.9 |
C24—C23—C22 | 119.61 (14) | C54—C53—H53A | 119.9 |
C24—C23—H23A | 120.2 | C53—C54—C55 | 120.43 (16) |
C22—C23—H23A | 120.2 | C53—C54—H54A | 119.8 |
C23—C24—C25 | 120.31 (15) | C55—C54—H54A | 119.8 |
C23—C24—H24A | 119.8 | C54—C55—C50 | 119.89 (14) |
C25—C24—H24A | 119.8 | C54—C55—H55A | 120.1 |
C20—C25—C24 | 120.73 (14) | C50—C55—H55A | 120.1 |
C20—C25—H25A | 119.6 | ||
C33—N1—C1—C2 | −176.81 (10) | C32—C27—C28—C29 | 1.02 (19) |
C17—N1—C1—C2 | −54.71 (13) | C26—C27—C28—C29 | −176.57 (12) |
C49—N1—C1—C2 | 64.73 (13) | C27—C28—C29—C30 | 0.2 (2) |
C3—N2—C2—C1 | −173.21 (10) | C28—C29—C30—C31 | −1.2 (2) |
C10—N2—C2—C1 | 66.67 (13) | C29—C30—C31—C32 | 1.0 (2) |
N1—C1—C2—N2 | 89.86 (13) | C30—C31—C32—C27 | 0.3 (2) |
C2—N2—C3—C4 | 172.35 (10) | C28—C27—C32—C31 | −1.26 (19) |
C10—N2—C3—C4 | −66.04 (14) | C26—C27—C32—C31 | 176.32 (12) |
N2—C3—C4—C9 | 138.46 (12) | C17—N1—C33—C34 | −55.26 (13) |
N2—C3—C4—C5 | −45.36 (17) | C1—N1—C33—C34 | 63.76 (13) |
C9—C4—C5—C6 | −0.1 (2) | C49—N1—C33—C34 | −175.49 (10) |
C3—C4—C5—C6 | −176.38 (14) | C42—N4—C34—C33 | 132.65 (11) |
C4—C5—C6—C7 | 0.7 (2) | C35—N4—C34—C33 | −96.66 (13) |
C5—C6—C7—C8 | −0.4 (3) | N1—C33—C34—N4 | 175.70 (10) |
C6—C7—C8—C9 | −0.4 (2) | C34—N4—C35—C36 | 159.68 (11) |
C7—C8—C9—C4 | 1.0 (2) | C42—N4—C35—C36 | −69.75 (15) |
C5—C4—C9—C8 | −0.7 (2) | N4—C35—C36—C41 | 117.24 (14) |
C3—C4—C9—C8 | 175.57 (13) | N4—C35—C36—C37 | −61.53 (16) |
C2—N2—C10—C11 | −87.12 (13) | C41—C36—C37—C38 | 0.0 (2) |
C3—N2—C10—C11 | 154.70 (11) | C35—C36—C37—C38 | 178.78 (13) |
N2—C10—C11—C12 | 127.04 (13) | C36—C37—C38—C39 | 0.7 (2) |
N2—C10—C11—C16 | −55.22 (17) | C37—C38—C39—C40 | −0.9 (2) |
C16—C11—C12—C13 | 0.27 (19) | C38—C39—C40—C41 | 0.6 (2) |
C10—C11—C12—C13 | 178.07 (12) | C37—C36—C41—C40 | −0.3 (2) |
C11—C12—C13—C14 | 0.3 (2) | C35—C36—C41—C40 | −179.06 (13) |
C12—C13—C14—C15 | −0.5 (2) | C39—C40—C41—C36 | 0.0 (2) |
C13—C14—C15—C16 | 0.0 (2) | C34—N4—C42—C43 | −75.77 (15) |
C14—C15—C16—C11 | 0.6 (2) | C35—N4—C42—C43 | 153.65 (12) |
C12—C11—C16—C15 | −0.71 (19) | N4—C42—C43—C48 | −44.20 (18) |
C10—C11—C16—C15 | −178.50 (12) | N4—C42—C43—C44 | 138.73 (14) |
C33—N1—C17—C18 | −56.95 (13) | C48—C43—C44—C45 | −1.9 (2) |
C1—N1—C17—C18 | −176.14 (10) | C42—C43—C44—C45 | 175.18 (14) |
C49—N1—C17—C18 | 62.73 (13) | C43—C44—C45—C46 | 0.2 (3) |
C19—N3—C18—C17 | 69.30 (13) | C44—C45—C46—C47 | 1.7 (3) |
C26—N3—C18—C17 | −170.33 (10) | C45—C46—C47—C48 | −1.9 (3) |
N1—C17—C18—N3 | 162.61 (10) | C44—C43—C48—C47 | 1.7 (3) |
C18—N3—C19—C20 | −163.59 (10) | C42—C43—C48—C47 | −175.40 (17) |
C26—N3—C19—C20 | 75.13 (13) | C46—C47—C48—C43 | 0.2 (3) |
N3—C19—C20—C25 | −144.93 (13) | C33—N1—C49—C50 | −68.30 (12) |
N3—C19—C20—C21 | 38.60 (17) | C17—N1—C49—C50 | 169.07 (10) |
C25—C20—C21—C22 | −0.6 (2) | C1—N1—C49—C50 | 50.26 (13) |
C19—C20—C21—C22 | 175.93 (13) | N1—C49—C50—C55 | 92.30 (14) |
C20—C21—C22—C23 | 0.2 (2) | N1—C49—C50—C51 | −90.69 (14) |
C21—C22—C23—C24 | 0.5 (2) | C55—C50—C51—C52 | −1.3 (2) |
C22—C23—C24—C25 | −0.7 (3) | C49—C50—C51—C52 | −178.31 (12) |
C21—C20—C25—C24 | 0.3 (2) | C50—C51—C52—C53 | 1.4 (2) |
C19—C20—C25—C24 | −176.25 (15) | C51—C52—C53—C54 | −0.8 (2) |
C23—C24—C25—C20 | 0.3 (3) | C52—C53—C54—C55 | 0.1 (2) |
C18—N3—C26—C27 | 67.15 (14) | C53—C54—C55—C50 | 0.0 (2) |
C19—N3—C26—C27 | −170.96 (11) | C51—C50—C55—C54 | 0.55 (19) |
N3—C26—C27—C32 | 70.99 (16) | C49—C50—C55—C54 | 177.60 (12) |
N3—C26—C27—C28 | −111.48 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
C39—H39A···I1i | 0.95 | 3.01 | 3.893 (2) | 154 |
C49—H49B···I1ii | 0.99 | 2.86 | 3.8187 (13) | 162 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C39—H39A···I1i | 0.95 | 3.01 | 3.893 (2) | 154 |
C49—H49B···I1ii | 0.99 | 2.86 | 3.8187 (13) | 162 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
Acknowledgements
SEB would like to acknowledge the NSF Graduate STEM Fellows in K-12 Education (GK-12) program (DGE-0742540) for support. This work was also partially supported by NSF grant CHE-0809393.
References
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Work in our laboratory has focused on the preparation of nonlinear polymers containing metal-metal bonds. Most recently, synthetic methods using the Huisgen 1,3-dipolar cycloaddition click reaction between 1,3,5-triethynylbenzene and an azide-functionalized molybdenum dimer, [(η5-C5H4(CH2)3N3)Mo(CO)3]2, have been used. It was concluded that 1,3,5-triethynylbenzene could not be coupled to azide functionalized molecules under click reaction conditions. 1,3,5-Triethynylbenzene reacted with Cp*Ru(COD)Cl instead of clicking, and Cu(IMes)Cl was too sterically bulky to catalyze three cycloadditions (Brady & Tyler, 2012). However, similar results demonstrated that [Cu(I)tren(C18H37)6]Br can catalyze the preparation of dendrimers by the Huisgen click reaction (Candelon et al., 2008; Barré et al., 2004). Dendritic analogues of the catalyst have also been prepared and used to synthesize second generation dendrimers with 54 terminal groups (Liang et al., 2011). These examples suggest that sterics do not effect the catalytic activity of [Cu(I)tren(C18H37)6]Br. This warranted the examination of [Cu(I)tren(C18H37)6]Br as a catalyst to prepare a star polymer with 1,3,5-triethynylbenzene.
The title compound (1) was prepared following literature preparations for [Cu(I)tren(C18H37)6]Br. Unfortunately, 1 did not coordinate to copper so it was not examined as a click chemistry catalyst.