research communications
κ4N]copper(II) bromide
of [tris(pyridin-2-ylmethyl)amine-aDepartment of Chemistry and Physics, Saint Mary's College, Notre Dame, IN 46556, USA, and bDepartment of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556, USA
*Correspondence e-mail: koshin@saintmarys.edu
In the 18H18N4)]Br, there are three crystallographically independent cations. One of the cations exhibits positional disorder of the pyridin-2-ylmethyl groups over two sets of sites with refined occupancies of 0.672 (8) and 0.328 (8). The outer-sphere bromine counter-ion is severely disordered over multiple sites. In each cation, the CuII ion is coordinated by the four N atoms of the tris(pyridin-2-ylmethyl)amine ligand and one bromine and adopts a slightly distorted trigonal–bipyramidal geometry.
of the title compound, [CuBr(CKeywords: crystal structure; five-coordinate copper(II) complex; Atom Transfer Radical Addition (ATRA); ligand disorder.
CCDC reference: 1478413
1. Chemical context
Atom Transfer Radical Addition (ATRA) reactions involve the formation of carbon–carbon bonds through the addition of saturated poly-halogenated hydrocarbons to ). First reported by Kharasch in the 1940s (Kharasch et al., 1945), the reaction incorporates halogen-group functionalities within products which can be used as starting reagents in further functionalization reactions (Iqbal et al., 1994). Subsequently, ATRA reactions have emerged as some of the most atom-economical methods for simultaneously forming C—C and C—X bonds, leading to the production of more attractive molecules (Eckenhoff & Pintauer, 2010). Most ATRA reactions proceed in the presence of a free-radical precursor or transition metal complex (catalyst), as the halogen-atom transfer agent and have been efficiently catalyzed by complexes incorporating nickel, ruthenium, iron, and copper (Eckenhoff et al., 2008). Studies suggest that the type of ligands used in ATRA reactions significantly influence the behavior of the catalyst generated due to different steric and electronic interactions with the metal atom (Matyjaszewski et al., 2001). Copper complexes made with tetradentate nitrogen-based ligands such as tris[2-(dimethylamino)ethyl]amine (Me6TREN), 1,4,8,11-tetraaza-1,4,8,11-tetramethylcyclotetradecane (Me6CYCLAM), and tris(pyridin-2-ylmethyl)amine (TPMA) are currently some of the most active multi-dentate ligand structures used in atom-transfer radical reactions (Tang et al., 2008). Given the significance and application of complexes made from these tetradentate ligands, we report on the synthesis and of the title compound [CuBr(C18H18N4)]Br (I) which incorporates tris(pyridin-2-ylmethyl)amine.
(Eckenhoff & Pintauer, 20102. Structural commentary
There are three crystallographically independent copper(II) atoms within the ). Each of the atoms adopts a slightly distorted trigonal–bipyramidal geometry and is coordinated by the four nitrogen atoms of the tris(pyridin-2-ylmethyl)amine ligand and one bromine atom (Table 1). The amine nitrogen and bromine atoms adopt the apical positions of the coordination environment and the pyridine nitrogen atoms are located in the equatorial plane. Derived metrics (bond lengths and angles) from the copper atoms to their respective coordinating atoms are typical (MOGUL analysis; Bruno et al., 2004). The τ-5 values for Cu1, Cu2 and Cu3 are 0.99, 0.99 and 0.89, respectively (Addison et al., 1984); the latter deviates the most from ideal geometry due to the disorder present in that molecule.
reported herein (Fig. 1
|
One of the three independent cations exhibits positional disorder of the pyridin-2-ylmethyl groups (see Refinement below for specific details). Despite this disorder, the connectivity is unequivocal. Unlike the polymorphic structure (Eckenhoff et al., 2008) that has crystallographically imposed symmetry on the pyridin-2-ylmethyl arms, the pyridin-2-ylmethyl groups on the cations reported here have geometries independent of the others. Furthermore, the structure here is mixture of Δ and Λ conformations of the ligand, whereas Eckenhoff's structure has chirally resolved upon crystallization.
3. Supramolecular features
The prominent feature of the crystal packing within this structure is the excessive positional disorder of the outer-sphere bromine anions. These are observed in a channel within the lattice (Fig. 2) that presumably has unresolvable solvent of crystallization also present. Because there are no prominent charge surfaces, packing is solely due to van der Waals interactions.
4. Database survey
There are six reported copper(II) bromide structures deposited in the Cambridge Structure Database incorporating the tris(pyridin-2-ylmethyl)amine ligand derivatives (Groom et al., 2016; CSD Version 5.37 plus one update). Of those six structures, one is a dimer incorporating two bridging bromine ligands (Maiti et al., 2007) and the remaining five are monomers. Out of the five monomer structures, three incorporate methyl or methoxy electron-withdrawing groups (Kaur et al., 2015), while one incorporates hydroxyl electron-donating groups (He et al., 2000). The final structure is a polymorph of that presented here: it incorporates an unsubstituted TPMA ligand framework but adopts a different (cubic, P213) and unit-cell parameters (a = 12.633 Å) due to lack of disorder in the ligand framework (Eckenhoff et al., 2008). Of the six total reported structures, four adopt similar distorted five-coordinate geometries as observed in complex (I), while two adopt a distorted six-coordinate geometry about the metal atom.
5. Synthesis and crystallization
Synthesis of tris(pyridin-2-ylmethyl)amine (TPMA) ligand: the TPMA ligand was synthesized according to modified literature procedures (Britovsek et al., 2005). A 500 mL round-bottom flask was charged with 100 mL of dichloromethane solvent. While mixing, 2-(aminomethyl)pyridine (1.62 mL, 15.0 mmol) and sodium triacetoxyborohydride (9.63 g, 44.2 mmol) were added, generating a clear-colored solution. 2-Pyridinecarboxaldehyde (3.38 g, 31.54 mmol) was slowly added to the mixture, producing a yellow-colored solution. The reaction was allowed to mix for 24 h and interrupted with the addition of sodium hydrogen carbonate until a pH of 10 was achieved. Extractions were performed on the resulting solution with ethyl acetate and the organic layers collected. The organic layer was subsequently dried using magnesium sulfate (MgSO4) and solvent removed using a rotary evaporator to generate a yellow residue. This residue was dried under vacuum for three h to produce the desired ligand as a yellow solid (4.43 g, 97%). 1H NMR (CDCl3, 400 MHz): δ3.86 (s, 2H), δ7.51 (d, 1H), δ7.63 (t, 1H), δ 8.52 (d, 1H). 13C NMR (CDCl3, 400 MHz): δ 60.60, 122.35, 123.32, 136.59, 149.35, 159.81. FT–IR (solid) v (cm−1): 3048 (s), 3009 (s), 2920 (s), 2803 (s), 1585 (s), 1566 (s), 970 (s), 745 (s).
Synthesis of tris(pyridin-2-ylmethyl)amine copper(II) bromide complex: TPMA (0.500 g, 1.72 mmol) was dissolved in 15 mL methanol in a 100 mL round-bottom flask. Copper(II) bromide (0.384 g, 1.72 mmol) was added to the flask to give a greenish-blue-colored solution. The reaction was allowed to mix for one hour then 30 mL of diethyl ether was transferred into the flask, facilitating the precipitation of the desired complex as a green powder. The mixture was filtered and the precipitate washed with excess diethyl ether solvent. The precipitate was dried under vacuum for 30 minutes to yield a green-colored solid (1.44 g, 94%). TOF–ESI–MS: (m/z) [M – (Br)]+ calculated for C18H18N4CuBr = 432.00, found 432.03. FT–IR (solid): v (cm−1) = 3337 (b), 2018 (s), 1600 (s), 1473 (s), 1426 (s), 1257 (s), 1150 (s), 1015 (s), 949 (s), 837 (s). UV–Vis: λmax (MeOH) = 700 nm. Green-colored single crystals suitable for X-ray analysis were obtained by slow diffusion of diethyl ether into a concentrated complex solution made in methanol.
6. Refinement
Crystal data, data collection and structure . The two ordered cations, the major occupancy component of the disordered cation and all outer-sphere bromine atoms were modeled with anisotropic atomic displacement parameters. The minor occupancy component of the disordered cation was modeled with isotropic atomic displacement parameters. Hydrogen atoms were included in geometrically calculated positions with C—H = 0.99 (methylene) and 0.95 Å (aromatic) and Uiso(H) = 1.2Ueq(C).
details are summarized in Table 2The disorder of the pyridin-2-ylmethyl groups was observed as residual electron density oriented in approximately a mirror to the major occupancy components. The occupancies of the two components were refined summed to unity, yielding an approximately 0.67:0.33 ratio. The pyridine rings for both components were constrained to an ideal hexagon, with C—C = 1.39 Å.
All of the outer-sphere, non-coordinating bromine counter-ions were found to be disordered over multiple sites. Initially, occupancies were refined freely to identify possible site pairings. One bromine (Br4) was found to be nearly fully located at one site. In subsequent A). Final residual electron density ranging from 8 to 13 e Å−3 was observed. Because an additional bromine was required for charge balance and there were no other counter-ions used during synthesis, it was assumed that the final bromine was disordered over multiple sites, presumably in concert with solvent from crystallization. Ultimately, seven locations were refined as partial-occupancy bromine atoms with a total occupancy summed to unity, yielding a 0.13:0.17:0.17:0.20:0.11:0.12:0.10 ratio of sites. The solvent contribution could not be reliably modeled.
cycles, residual density adjacent to the site was revealed and ultimately modeled as a bromine disordered over two sites with occupancies 0.80:0.20. Two bromine sites whose occupancies refined independently to nearly 50% were both set to 50% occupancy and assumed to be disorder of the same bromine atom (Br5/5Supporting information
CCDC reference: 1478413
https://doi.org/10.1107/S2056989016007568/lh5812sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016007568/lh5812Isup2.hkl
Data collection: APEX3 (Bruker, 2015); cell
SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT-2014/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: XP (Bruker, 2015); software used to prepare material for publication: publCIF (Westrip, 2010).[CuBr(C18H18N4)]Br | Z = 6 |
Mr = 513.72 | F(000) = 1518 |
Triclinic, P1 | Dx = 1.602 Mg m−3 |
a = 11.5415 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 15.2747 (9) Å | Cell parameters from 9798 reflections |
c = 19.9663 (12) Å | θ = 2.4–26.3° |
α = 88.425 (2)° | µ = 4.79 mm−1 |
β = 75.894 (2)° | T = 120 K |
γ = 69.650 (2)° | Block, green |
V = 3194.4 (3) Å3 | 0.30 × 0.30 × 0.26 mm |
Bruker APEXII diffractometer | 13032 independent reflections |
Radiation source: fine-focus sealed tube | 10550 reflections with I > 2σ(I) |
Detector resolution: 8.33 pixels mm-1 | Rint = 0.020 |
combination of ω and φ–scans | θmax = 26.4°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | h = −14→14 |
Tmin = 0.688, Tmax = 0.862 | k = −19→19 |
25682 measured reflections | l = −24→24 |
Refinement on F2 | Primary atom site location: real-space vector search |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.086 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.254 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.1449P)2 + 25.6015P] where P = (Fo2 + 2Fc2)/3 |
13032 reflections | (Δ/σ)max = 0.027 |
769 parameters | Δρmax = 3.78 e Å−3 |
1 restraint | Δρmin = −1.50 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. The outer sphere bromine anion atoms were all found to be disordered over multiple sites. Br4/4A was found to occupy two sites close to each other and was refined with occupancies summed to unity yielding an approximate 0.83:0.17 ratio. Br5/5A was modeled as two half occupancy bromine atoms from an initial, independent, refinement of the occupancies for these sites. Br6 is disordered over multiple sites. Occupancies of the sites were refined summed to unity yielding an approximately 0.14:0.17:0.17:0.20:0.11:0.12:0.09 ratio of site occupancies. Attempts to model this disorder as undifferentiated solvent did not meet with success. Furthermore, because the electron density associated with this is located within the enveloped developed by SQUEEZE, this routine could not be employed. The result is that there is some additional residual electron density that cannot be reliably accounted for. Presumably there is solvent of crystallization present at the sites when they are not occupied by anions. This was not modeled. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.29355 (9) | 0.21210 (6) | 0.12631 (5) | 0.0349 (2) | |
Br1 | 0.28112 (9) | 0.08631 (6) | 0.19713 (5) | 0.0542 (3) | |
N1 | 0.3062 (6) | 0.3198 (4) | 0.0645 (3) | 0.0357 (14) | |
N2 | 0.4733 (6) | 0.1456 (5) | 0.0635 (4) | 0.0431 (16) | |
N3 | 0.2663 (7) | 0.3099 (5) | 0.2015 (4) | 0.0418 (16) | |
N4 | 0.1495 (6) | 0.2241 (4) | 0.0789 (3) | 0.0337 (13) | |
C1 | 0.3979 (9) | 0.2781 (6) | −0.0032 (4) | 0.046 (2) | |
H1A | 0.4339 | 0.3246 | −0.0260 | 0.055* | |
H1B | 0.3527 | 0.2608 | −0.0340 | 0.055* | |
C2 | 0.5051 (8) | 0.1917 (6) | 0.0084 (5) | 0.046 (2) | |
C3 | 0.6262 (10) | 0.1613 (8) | −0.0350 (6) | 0.063 (3) | |
H3 | 0.6477 | 0.1957 | −0.0734 | 0.076* | |
C4 | 0.7151 (10) | 0.0802 (9) | −0.0217 (8) | 0.080 (4) | |
H4 | 0.7995 | 0.0590 | −0.0506 | 0.096* | |
C5 | 0.6831 (10) | 0.0305 (8) | 0.0323 (7) | 0.069 (3) | |
H5 | 0.7430 | −0.0270 | 0.0405 | 0.082* | |
C6 | 0.5597 (8) | 0.0659 (7) | 0.0757 (5) | 0.051 (2) | |
H6 | 0.5368 | 0.0326 | 0.1146 | 0.061* | |
C7 | 0.3496 (9) | 0.3801 (6) | 0.1005 (4) | 0.0426 (18) | |
H7A | 0.3277 | 0.4429 | 0.0819 | 0.051* | |
H7B | 0.4434 | 0.3530 | 0.0934 | 0.051* | |
C8 | 0.2855 (8) | 0.3877 (6) | 0.1763 (4) | 0.0413 (18) | |
C9 | 0.2535 (10) | 0.4680 (7) | 0.2179 (5) | 0.057 (2) | |
H9 | 0.2657 | 0.5227 | 0.1988 | 0.068* | |
C10 | 0.2035 (11) | 0.4664 (8) | 0.2878 (5) | 0.063 (3) | |
H10 | 0.1798 | 0.5206 | 0.3176 | 0.075* | |
C11 | 0.1881 (11) | 0.3863 (9) | 0.3143 (5) | 0.065 (3) | |
H11 | 0.1563 | 0.3841 | 0.3626 | 0.078* | |
C12 | 0.2189 (10) | 0.3083 (8) | 0.2701 (5) | 0.055 (2) | |
H12 | 0.2065 | 0.2533 | 0.2884 | 0.066* | |
C13 | 0.1770 (8) | 0.3701 (6) | 0.0540 (4) | 0.0396 (17) | |
H13A | 0.1834 | 0.4080 | 0.0131 | 0.048* | |
H13B | 0.1233 | 0.4128 | 0.0949 | 0.048* | |
C14 | 0.1174 (8) | 0.3004 (5) | 0.0431 (4) | 0.0365 (16) | |
C15 | 0.0359 (9) | 0.3132 (7) | 0.0003 (4) | 0.047 (2) | |
H15 | 0.0122 | 0.3689 | −0.0235 | 0.056* | |
C16 | −0.0100 (8) | 0.2432 (7) | −0.0068 (4) | 0.050 (2) | |
H16 | −0.0625 | 0.2485 | −0.0379 | 0.060* | |
C17 | 0.0196 (9) | 0.1657 (7) | 0.0305 (4) | 0.0453 (19) | |
H17 | −0.0135 | 0.1176 | 0.0267 | 0.054* | |
C18 | 0.0975 (8) | 0.1589 (6) | 0.0734 (4) | 0.0407 (18) | |
H18 | 0.1159 | 0.1061 | 0.1005 | 0.049* | |
Cu2 | 0.78574 (9) | 1.03414 (6) | 0.22801 (5) | 0.0341 (2) | |
Br2 | 0.94552 (9) | 0.97310 (6) | 0.12441 (4) | 0.0507 (3) | |
N5 | 0.6517 (6) | 1.0824 (5) | 0.3189 (3) | 0.0366 (14) | |
N6 | 0.7077 (6) | 1.1724 (4) | 0.2059 (3) | 0.0346 (13) | |
N7 | 0.9054 (6) | 1.0078 (4) | 0.2935 (3) | 0.0345 (13) | |
N8 | 0.6826 (7) | 0.9480 (4) | 0.2270 (4) | 0.0428 (16) | |
C19 | 0.6282 (9) | 1.1832 (6) | 0.3303 (5) | 0.046 (2) | |
H19A | 0.6920 | 1.1906 | 0.3528 | 0.055* | |
H19B | 0.5424 | 1.2139 | 0.3615 | 0.055* | |
C20 | 0.6366 (7) | 1.2294 (5) | 0.2629 (4) | 0.0374 (17) | |
C21 | 0.5785 (8) | 1.3247 (6) | 0.2589 (5) | 0.047 (2) | |
H21 | 0.5261 | 1.3640 | 0.2990 | 0.056* | |
C22 | 0.5998 (9) | 1.3609 (6) | 0.1940 (5) | 0.051 (2) | |
H22 | 0.5631 | 1.4263 | 0.1899 | 0.061* | |
C23 | 0.6724 (9) | 1.3040 (6) | 0.1362 (5) | 0.048 (2) | |
H23 | 0.6865 | 1.3288 | 0.0920 | 0.058* | |
C24 | 0.7246 (8) | 1.2095 (6) | 0.1439 (5) | 0.0415 (18) | |
H24 | 0.7743 | 1.1691 | 0.1040 | 0.050* | |
C25 | 0.7049 (8) | 1.0265 (7) | 0.3737 (4) | 0.0457 (19) | |
H25A | 0.6898 | 0.9664 | 0.3753 | 0.055* | |
H25B | 0.6613 | 1.0611 | 0.4194 | 0.055* | |
C26 | 0.8459 (8) | 1.0079 (6) | 0.3590 (4) | 0.0407 (18) | |
C27 | 0.9092 (10) | 0.9863 (7) | 0.4114 (5) | 0.052 (2) | |
H27 | 0.8644 | 0.9841 | 0.4578 | 0.062* | |
C28 | 1.0400 (11) | 0.9678 (8) | 0.3942 (6) | 0.061 (3) | |
H28 | 1.0858 | 0.9550 | 0.4291 | 0.074* | |
C29 | 1.1022 (10) | 0.9683 (7) | 0.3262 (6) | 0.057 (2) | |
H29 | 1.1919 | 0.9542 | 0.3135 | 0.068* | |
C30 | 1.0333 (9) | 0.9894 (6) | 0.2762 (5) | 0.0443 (19) | |
H30 | 1.0761 | 0.9910 | 0.2293 | 0.053* | |
C31 | 0.5351 (8) | 1.0677 (6) | 0.3124 (5) | 0.048 (2) | |
H31A | 0.4885 | 1.1177 | 0.2860 | 0.057* | |
H31B | 0.4784 | 1.0701 | 0.3589 | 0.057* | |
C32 | 0.5716 (8) | 0.9739 (6) | 0.2755 (6) | 0.055 (3) | |
C33 | 0.4913 (10) | 0.9229 (8) | 0.2883 (10) | 0.093 (5) | |
H33 | 0.4125 | 0.9444 | 0.3224 | 0.112* | |
C34 | 0.5301 (13) | 0.8390 (9) | 0.2492 (12) | 0.128 (8) | |
H34 | 0.4785 | 0.8011 | 0.2567 | 0.154* | |
C35 | 0.6430 (12) | 0.8119 (7) | 0.2002 (9) | 0.085 (5) | |
H35 | 0.6709 | 0.7546 | 0.1733 | 0.102* | |
C36 | 0.7173 (11) | 0.8676 (6) | 0.1895 (6) | 0.058 (3) | |
H36 | 0.7951 | 0.8483 | 0.1545 | 0.069* | |
Cu3 | 0.78179 (9) | 0.55333 (7) | 0.25199 (4) | 0.0332 (2) | |
Br3 | 0.84691 (9) | 0.53090 (6) | 0.12962 (4) | 0.0474 (2) | |
N9 | 0.7248 (6) | 0.5733 (5) | 0.3575 (3) | 0.0336 (13) | |
C37 | 0.6067 (11) | 0.5541 (8) | 0.3805 (6) | 0.036 (3) | 0.672 (8) |
H37A | 0.5608 | 0.5841 | 0.4274 | 0.043* | 0.672 (8) |
H37B | 0.6266 | 0.4858 | 0.3830 | 0.043* | 0.672 (8) |
C38 | 0.5254 (6) | 0.5897 (6) | 0.3329 (3) | 0.040 (3) | 0.672 (8) |
C39 | 0.3929 (7) | 0.6198 (7) | 0.3517 (4) | 0.048 (3) | 0.672 (8) |
H39 | 0.3490 | 0.6207 | 0.3987 | 0.058* | 0.672 (8) |
C40 | 0.3247 (6) | 0.6484 (7) | 0.3016 (6) | 0.059 (4) | 0.672 (8) |
H40 | 0.2341 | 0.6690 | 0.3144 | 0.071* | 0.672 (8) |
C41 | 0.3889 (10) | 0.6470 (9) | 0.2328 (5) | 0.073 (9) | 0.672 (8) |
H41 | 0.3423 | 0.6666 | 0.1986 | 0.087* | 0.672 (8) |
C42 | 0.5214 (10) | 0.6170 (8) | 0.2140 (3) | 0.064 (11) | 0.672 (8) |
H42 | 0.5653 | 0.6160 | 0.1670 | 0.077* | 0.672 (8) |
N10 | 0.5897 (6) | 0.5883 (6) | 0.2641 (4) | 0.036 (2) | 0.672 (8) |
C43 | 0.7222 (10) | 0.6622 (8) | 0.3746 (6) | 0.033 (2) | 0.672 (8) |
H43A | 0.7308 | 0.6644 | 0.4226 | 0.040* | 0.672 (8) |
H43B | 0.6388 | 0.7092 | 0.3727 | 0.040* | 0.672 (8) |
C44 | 0.8253 (9) | 0.6864 (6) | 0.3276 (4) | 0.036 (3) | 0.672 (8) |
C45 | 0.8754 (10) | 0.7504 (6) | 0.3455 (5) | 0.047 (3) | 0.672 (8) |
H45 | 0.8435 | 0.7812 | 0.3904 | 0.056* | 0.672 (8) |
C46 | 0.9721 (10) | 0.7694 (7) | 0.2977 (7) | 0.049 (5) | 0.672 (8) |
H46 | 1.0064 | 0.8131 | 0.3099 | 0.059* | 0.672 (8) |
C47 | 1.0188 (10) | 0.7243 (10) | 0.2320 (6) | 0.043 (5) | 0.672 (8) |
H47 | 1.0849 | 0.7373 | 0.1993 | 0.052* | 0.672 (8) |
C48 | 0.9687 (12) | 0.6603 (10) | 0.2141 (4) | 0.043 (5) | 0.672 (8) |
H48 | 1.0005 | 0.6295 | 0.1691 | 0.052* | 0.672 (8) |
N11 | 0.8719 (11) | 0.6413 (7) | 0.2618 (5) | 0.038 (4) | 0.672 (8) |
C49 | 0.8310 (12) | 0.4950 (8) | 0.3817 (6) | 0.035 (2) | 0.672 (8) |
H49A | 0.9063 | 0.5142 | 0.3762 | 0.042* | 0.672 (8) |
H49B | 0.8000 | 0.4871 | 0.4315 | 0.042* | 0.672 (8) |
C50 | 0.8702 (8) | 0.4041 (4) | 0.3422 (3) | 0.036 (3) | 0.672 (8) |
C51 | 0.9133 (9) | 0.3163 (5) | 0.3678 (3) | 0.041 (3) | 0.672 (8) |
H51 | 0.9169 | 0.3109 | 0.4148 | 0.049* | 0.672 (8) |
C52 | 0.9512 (9) | 0.2362 (4) | 0.3246 (5) | 0.046 (3) | 0.672 (8) |
H52 | 0.9807 | 0.1762 | 0.3421 | 0.055* | 0.672 (8) |
C53 | 0.9460 (11) | 0.2441 (5) | 0.2558 (4) | 0.045 (4) | 0.672 (8) |
H53 | 0.9719 | 0.1894 | 0.2263 | 0.053* | 0.672 (8) |
C54 | 0.9028 (12) | 0.3319 (7) | 0.2302 (3) | 0.051 (5) | 0.672 (8) |
H54 | 0.8992 | 0.3373 | 0.1831 | 0.061* | 0.672 (8) |
N12 | 0.8649 (10) | 0.4120 (5) | 0.2734 (4) | 0.031 (2) | 0.672 (8) |
C37A | 0.5973 (18) | 0.6729 (13) | 0.3737 (10) | 0.023 (4)* | 0.328 (8) |
H37C | 0.5488 | 0.6781 | 0.4226 | 0.028* | 0.328 (8) |
H37D | 0.6252 | 0.7275 | 0.3653 | 0.028* | 0.328 (8) |
C38A | 0.5180 (11) | 0.6709 (10) | 0.3282 (6) | 0.025 (4)* | 0.328 (8) |
C39A | 0.3857 (11) | 0.7107 (10) | 0.3429 (6) | 0.040 (6)* | 0.328 (8) |
H39A | 0.3389 | 0.7423 | 0.3867 | 0.048* | 0.328 (8) |
C40A | 0.3221 (9) | 0.7041 (12) | 0.2935 (7) | 0.030 (5)* | 0.328 (8) |
H40A | 0.2317 | 0.7313 | 0.3036 | 0.036* | 0.328 (8) |
C41A | 0.3907 (12) | 0.6578 (13) | 0.2294 (6) | 0.026 (7)* | 0.328 (8) |
H41A | 0.3472 | 0.6534 | 0.1957 | 0.031* | 0.328 (8) |
C42A | 0.5229 (12) | 0.6180 (10) | 0.2147 (5) | 0.012 (8)* | 0.328 (8) |
H42A | 0.5698 | 0.5864 | 0.1709 | 0.015* | 0.328 (8) |
N10A | 0.5866 (9) | 0.6246 (8) | 0.2641 (6) | 0.017 (4)* | 0.328 (8) |
C43A | 0.8177 (18) | 0.6049 (14) | 0.3841 (10) | 0.023 (4)* | 0.328 (8) |
H43C | 0.7719 | 0.6422 | 0.4285 | 0.028* | 0.328 (8) |
H43D | 0.8860 | 0.5489 | 0.3934 | 0.028* | 0.328 (8) |
C44A | 0.8751 (18) | 0.6595 (12) | 0.3373 (8) | 0.032 (6)* | 0.328 (8) |
C45A | 0.9284 (19) | 0.7224 (13) | 0.3536 (7) | 0.026 (5)* | 0.328 (8) |
H45A | 0.9212 | 0.7376 | 0.4006 | 0.031* | 0.328 (8) |
C46A | 0.992 (2) | 0.7630 (15) | 0.3010 (11) | 0.041 (9)* | 0.328 (8) |
H46A | 1.0286 | 0.8060 | 0.3122 | 0.049* | 0.328 (8) |
C47A | 1.003 (2) | 0.7407 (19) | 0.2323 (9) | 0.031 (8)* | 0.328 (8) |
H47A | 1.0463 | 0.7685 | 0.1964 | 0.037* | 0.328 (8) |
C48A | 0.949 (3) | 0.6778 (18) | 0.2160 (7) | 0.019 (6)* | 0.328 (8) |
H48A | 0.9565 | 0.6626 | 0.1690 | 0.023* | 0.328 (8) |
N11A | 0.886 (2) | 0.6372 (13) | 0.2685 (10) | 0.016 (6)* | 0.328 (8) |
C49A | 0.6874 (19) | 0.5069 (14) | 0.3899 (10) | 0.023 (4)* | 0.328 (8) |
H49C | 0.5988 | 0.5162 | 0.3885 | 0.028* | 0.328 (8) |
H49D | 0.6915 | 0.5074 | 0.4389 | 0.028* | 0.328 (8) |
C50A | 0.7774 (15) | 0.4172 (9) | 0.3521 (7) | 0.028 (4)* | 0.328 (8) |
C51A | 0.8117 (16) | 0.3309 (10) | 0.3808 (6) | 0.042 (6)* | 0.328 (8) |
H51A | 0.7801 | 0.3263 | 0.4289 | 0.051* | 0.328 (8) |
C52A | 0.8923 (17) | 0.2511 (8) | 0.3392 (8) | 0.040 (7)* | 0.328 (8) |
H52A | 0.9157 | 0.1920 | 0.3588 | 0.048* | 0.328 (8) |
C53A | 0.9385 (18) | 0.2577 (10) | 0.2688 (8) | 0.027 (6)* | 0.328 (8) |
H53A | 0.9935 | 0.2031 | 0.2403 | 0.032* | 0.328 (8) |
C54A | 0.9041 (17) | 0.3441 (13) | 0.2401 (6) | 0.009 (4)* | 0.328 (8) |
H54A | 0.9357 | 0.3486 | 0.1920 | 0.011* | 0.328 (8) |
N12A | 0.8236 (15) | 0.4238 (10) | 0.2818 (7) | 0.027 (6)* | 0.328 (8) |
Br4 | 0.2753 (9) | 0.6342 (2) | 0.06977 (13) | 0.0424 (9) | 0.80 (4) |
Br4A | 0.320 (5) | 0.626 (2) | 0.0748 (10) | 0.046 (6) | 0.20 (4) |
Br5 | 0.9243 (4) | 0.4418 (2) | 0.53149 (17) | 0.1024 (11) | 0.5 |
Br5A | 0.66590 (18) | 0.18484 (14) | 0.53556 (10) | 0.0538 (5) | 0.5 |
Br6A | 0.6049 (11) | 0.0709 (6) | 0.5606 (3) | 0.083 (4) | 0.136 (3) |
Br6B | 0.3821 (5) | 0.4517 (7) | 0.4322 (2) | 0.085 (3) | 0.171 (3) |
Br6C | 0.8053 (6) | −0.1392 (5) | 0.5725 (4) | 0.059 (2) | 0.167 (3) |
Br6D | 0.7729 (6) | −0.1886 (7) | 0.5463 (3) | 0.090 (3) | 0.198 (3) |
Br6E | 0.4331 (9) | 0.1069 (7) | 0.5323 (4) | 0.053 (3) | 0.107 (3) |
Br6F | 0.5711 (7) | 0.5148 (6) | 0.0703 (4) | 0.051 (2) | 0.125 (3) |
Br6G | 1.0726 (13) | 0.7636 (11) | 0.4667 (8) | 0.078 (4) | 0.096 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0329 (5) | 0.0306 (5) | 0.0386 (5) | −0.0070 (4) | −0.0112 (4) | 0.0110 (4) |
Br1 | 0.0519 (5) | 0.0450 (5) | 0.0618 (6) | −0.0129 (4) | −0.0160 (4) | 0.0285 (4) |
N1 | 0.044 (4) | 0.033 (3) | 0.032 (3) | −0.016 (3) | −0.009 (3) | 0.005 (3) |
N2 | 0.034 (3) | 0.041 (4) | 0.052 (4) | −0.010 (3) | −0.011 (3) | 0.000 (3) |
N3 | 0.043 (4) | 0.047 (4) | 0.038 (4) | −0.011 (3) | −0.023 (3) | 0.010 (3) |
N4 | 0.036 (3) | 0.033 (3) | 0.029 (3) | −0.009 (3) | −0.008 (2) | 0.002 (2) |
C1 | 0.049 (5) | 0.049 (5) | 0.038 (4) | −0.022 (4) | 0.000 (4) | 0.001 (4) |
C2 | 0.043 (5) | 0.044 (5) | 0.053 (5) | −0.021 (4) | −0.006 (4) | −0.004 (4) |
C3 | 0.060 (6) | 0.059 (6) | 0.068 (7) | −0.031 (5) | 0.007 (5) | −0.011 (5) |
C4 | 0.039 (5) | 0.065 (7) | 0.117 (11) | −0.016 (5) | 0.015 (6) | −0.020 (7) |
C5 | 0.043 (5) | 0.056 (6) | 0.094 (9) | −0.001 (5) | −0.015 (5) | −0.006 (6) |
C6 | 0.038 (4) | 0.047 (5) | 0.063 (6) | −0.007 (4) | −0.016 (4) | −0.001 (4) |
C7 | 0.051 (5) | 0.037 (4) | 0.046 (5) | −0.018 (4) | −0.018 (4) | 0.011 (3) |
C8 | 0.046 (4) | 0.043 (4) | 0.045 (5) | −0.017 (4) | −0.027 (4) | 0.008 (3) |
C9 | 0.067 (6) | 0.054 (6) | 0.055 (6) | −0.014 (5) | −0.034 (5) | −0.003 (4) |
C10 | 0.074 (7) | 0.069 (7) | 0.047 (5) | −0.014 (5) | −0.033 (5) | −0.008 (5) |
C11 | 0.064 (6) | 0.094 (9) | 0.039 (5) | −0.018 (6) | −0.026 (5) | −0.004 (5) |
C12 | 0.065 (6) | 0.069 (6) | 0.039 (5) | −0.023 (5) | −0.027 (4) | 0.011 (4) |
C13 | 0.047 (4) | 0.035 (4) | 0.033 (4) | −0.005 (3) | −0.017 (3) | 0.005 (3) |
C14 | 0.040 (4) | 0.036 (4) | 0.028 (4) | −0.006 (3) | −0.010 (3) | 0.002 (3) |
C15 | 0.050 (5) | 0.054 (5) | 0.031 (4) | −0.005 (4) | −0.020 (4) | 0.009 (4) |
C16 | 0.041 (5) | 0.073 (6) | 0.035 (4) | −0.015 (4) | −0.014 (4) | −0.007 (4) |
C17 | 0.048 (5) | 0.056 (5) | 0.034 (4) | −0.025 (4) | −0.004 (3) | −0.008 (4) |
C18 | 0.041 (4) | 0.047 (5) | 0.031 (4) | −0.015 (4) | −0.003 (3) | −0.002 (3) |
Cu2 | 0.0355 (5) | 0.0312 (5) | 0.0343 (5) | −0.0097 (4) | −0.0087 (4) | −0.0037 (4) |
Br2 | 0.0523 (5) | 0.0471 (5) | 0.0380 (5) | −0.0038 (4) | −0.0037 (4) | −0.0084 (4) |
N5 | 0.033 (3) | 0.039 (3) | 0.038 (3) | −0.014 (3) | −0.007 (3) | −0.002 (3) |
N6 | 0.030 (3) | 0.030 (3) | 0.042 (4) | −0.008 (2) | −0.009 (3) | −0.006 (3) |
N7 | 0.035 (3) | 0.034 (3) | 0.038 (3) | −0.016 (3) | −0.011 (3) | 0.003 (3) |
N8 | 0.046 (4) | 0.026 (3) | 0.064 (5) | −0.007 (3) | −0.034 (4) | 0.003 (3) |
C19 | 0.046 (5) | 0.043 (5) | 0.045 (5) | −0.014 (4) | −0.007 (4) | −0.011 (4) |
C20 | 0.032 (4) | 0.035 (4) | 0.047 (4) | −0.014 (3) | −0.008 (3) | −0.002 (3) |
C21 | 0.038 (4) | 0.040 (4) | 0.058 (5) | −0.008 (4) | −0.011 (4) | −0.011 (4) |
C22 | 0.049 (5) | 0.034 (4) | 0.070 (6) | −0.010 (4) | −0.020 (4) | 0.000 (4) |
C23 | 0.050 (5) | 0.034 (4) | 0.059 (5) | −0.013 (4) | −0.013 (4) | 0.009 (4) |
C24 | 0.037 (4) | 0.039 (4) | 0.045 (5) | −0.011 (3) | −0.007 (3) | 0.001 (3) |
C25 | 0.042 (4) | 0.051 (5) | 0.038 (4) | −0.013 (4) | −0.005 (3) | 0.000 (4) |
C26 | 0.047 (5) | 0.036 (4) | 0.042 (4) | −0.014 (3) | −0.017 (4) | 0.001 (3) |
C27 | 0.063 (6) | 0.054 (5) | 0.038 (5) | −0.014 (4) | −0.023 (4) | 0.011 (4) |
C28 | 0.076 (7) | 0.062 (6) | 0.065 (7) | −0.031 (5) | −0.042 (6) | 0.015 (5) |
C29 | 0.054 (6) | 0.057 (6) | 0.073 (7) | −0.026 (5) | −0.032 (5) | 0.014 (5) |
C30 | 0.048 (5) | 0.039 (4) | 0.056 (5) | −0.024 (4) | −0.020 (4) | 0.011 (4) |
C31 | 0.030 (4) | 0.043 (5) | 0.066 (6) | −0.013 (3) | −0.007 (4) | 0.001 (4) |
C32 | 0.034 (4) | 0.035 (4) | 0.110 (8) | −0.011 (4) | −0.044 (5) | 0.011 (5) |
C33 | 0.031 (5) | 0.054 (6) | 0.200 (17) | −0.011 (5) | −0.045 (7) | −0.001 (8) |
C34 | 0.057 (8) | 0.049 (7) | 0.30 (3) | −0.019 (6) | −0.089 (12) | −0.016 (10) |
C35 | 0.069 (8) | 0.040 (5) | 0.159 (14) | −0.002 (5) | −0.073 (9) | −0.022 (7) |
C36 | 0.071 (6) | 0.029 (4) | 0.084 (7) | −0.006 (4) | −0.058 (6) | 0.000 (4) |
Cu3 | 0.0383 (5) | 0.0402 (5) | 0.0208 (4) | −0.0115 (4) | −0.0105 (3) | 0.0043 (3) |
Br3 | 0.0607 (5) | 0.0542 (5) | 0.0224 (4) | −0.0158 (4) | −0.0081 (3) | 0.0019 (3) |
N9 | 0.034 (3) | 0.051 (4) | 0.023 (3) | −0.020 (3) | −0.014 (2) | 0.004 (3) |
C37 | 0.042 (6) | 0.035 (6) | 0.026 (5) | −0.012 (5) | −0.003 (4) | −0.002 (4) |
C38 | 0.044 (6) | 0.034 (6) | 0.042 (7) | −0.010 (5) | −0.018 (5) | −0.008 (5) |
C39 | 0.037 (6) | 0.046 (7) | 0.060 (8) | −0.006 (5) | −0.019 (6) | −0.013 (6) |
C40 | 0.043 (8) | 0.054 (9) | 0.085 (12) | −0.012 (6) | −0.033 (8) | −0.007 (8) |
C41 | 0.078 (14) | 0.065 (12) | 0.100 (18) | −0.026 (9) | −0.067 (13) | 0.001 (10) |
C42 | 0.10 (2) | 0.043 (10) | 0.078 (16) | −0.032 (9) | −0.067 (14) | 0.009 (7) |
N10 | 0.053 (6) | 0.028 (6) | 0.033 (5) | −0.014 (4) | −0.021 (4) | −0.005 (4) |
C43 | 0.034 (6) | 0.033 (6) | 0.029 (5) | −0.005 (4) | −0.011 (4) | −0.002 (4) |
C44 | 0.049 (7) | 0.031 (6) | 0.030 (6) | −0.009 (5) | −0.018 (5) | 0.004 (4) |
C45 | 0.035 (7) | 0.042 (7) | 0.057 (8) | 0.002 (6) | −0.020 (6) | −0.007 (6) |
C46 | 0.031 (7) | 0.030 (7) | 0.082 (13) | −0.005 (5) | −0.013 (7) | −0.002 (6) |
C47 | 0.024 (6) | 0.032 (7) | 0.065 (10) | 0.001 (6) | −0.014 (6) | 0.018 (6) |
C48 | 0.032 (8) | 0.030 (8) | 0.054 (9) | 0.006 (6) | −0.014 (6) | 0.016 (5) |
N11 | 0.040 (7) | 0.038 (7) | 0.028 (6) | −0.003 (5) | −0.008 (5) | 0.000 (4) |
C49 | 0.047 (6) | 0.031 (5) | 0.027 (5) | −0.010 (5) | −0.018 (5) | 0.002 (4) |
C50 | 0.038 (6) | 0.036 (6) | 0.028 (5) | −0.002 (5) | −0.012 (4) | 0.000 (4) |
C51 | 0.041 (7) | 0.043 (7) | 0.034 (6) | −0.008 (5) | −0.010 (5) | 0.013 (5) |
C52 | 0.049 (8) | 0.036 (6) | 0.041 (7) | −0.011 (6) | 0.001 (6) | 0.005 (5) |
C53 | 0.041 (7) | 0.034 (7) | 0.054 (8) | −0.010 (5) | −0.008 (6) | −0.007 (6) |
C54 | 0.051 (9) | 0.049 (9) | 0.052 (9) | −0.016 (7) | −0.011 (7) | −0.018 (7) |
N12 | 0.032 (6) | 0.035 (6) | 0.025 (5) | −0.008 (5) | −0.010 (4) | 0.005 (4) |
Br4 | 0.043 (2) | 0.0419 (7) | 0.0400 (7) | −0.0046 (8) | −0.0224 (8) | 0.0031 (5) |
Br4A | 0.055 (12) | 0.051 (6) | 0.040 (4) | −0.028 (7) | −0.011 (5) | 0.002 (4) |
Br5 | 0.119 (2) | 0.106 (2) | 0.0821 (19) | −0.060 (2) | 0.0087 (17) | −0.0372 (17) |
Br5A | 0.0488 (10) | 0.0572 (11) | 0.0579 (11) | −0.0253 (8) | −0.0048 (8) | −0.0256 (9) |
Br6A | 0.164 (9) | 0.078 (5) | 0.015 (3) | −0.090 (6) | 0.034 (4) | −0.004 (3) |
Br6B | 0.037 (3) | 0.206 (9) | 0.010 (2) | −0.043 (4) | −0.0021 (18) | 0.001 (3) |
Br6C | 0.053 (3) | 0.075 (4) | 0.048 (4) | −0.036 (3) | 0.006 (3) | 0.021 (3) |
Br6D | 0.054 (3) | 0.139 (7) | 0.023 (2) | 0.023 (4) | 0.004 (2) | −0.005 (3) |
Br6E | 0.056 (5) | 0.070 (6) | 0.042 (4) | −0.044 (5) | 0.006 (4) | 0.001 (4) |
Br6F | 0.048 (4) | 0.060 (5) | 0.048 (4) | −0.017 (3) | −0.018 (3) | −0.007 (3) |
Br6G | 0.070 (8) | 0.102 (10) | 0.088 (9) | −0.050 (7) | −0.042 (7) | 0.051 (8) |
Cu1—N3 | 2.037 (7) | C36—H36 | 0.9500 |
Cu1—N1 | 2.054 (6) | Cu3—N12A | 1.977 (12) |
Cu1—N4 | 2.060 (6) | Cu3—N11 | 2.004 (10) |
Cu1—N2 | 2.060 (7) | Cu3—N10 | 2.045 (7) |
Cu1—Br1 | 2.3781 (12) | Cu3—N9 | 2.046 (6) |
N1—C7 | 1.465 (11) | Cu3—N10A | 2.088 (9) |
N1—C13 | 1.485 (10) | Cu3—N11A | 2.114 (17) |
N1—C1 | 1.495 (10) | Cu3—N12 | 2.115 (6) |
N2—C2 | 1.335 (12) | Cu3—Br3 | 2.3715 (11) |
N2—C6 | 1.339 (11) | N9—C49A | 1.33 (2) |
N3—C8 | 1.346 (11) | N9—C43 | 1.398 (13) |
N3—C12 | 1.347 (12) | N9—C37 | 1.456 (13) |
N4—C14 | 1.337 (10) | N9—C43A | 1.52 (2) |
N4—C18 | 1.348 (11) | N9—C49 | 1.551 (12) |
C1—C2 | 1.521 (13) | N9—C37A | 1.68 (2) |
C1—H1A | 0.9900 | C37—C38 | 1.459 (13) |
C1—H1B | 0.9900 | C37—H37A | 0.9900 |
C2—C3 | 1.379 (13) | C37—H37B | 0.9900 |
C3—C4 | 1.374 (18) | C38—C39 | 1.3900 |
C3—H3 | 0.9500 | C38—N10 | 1.3900 |
C4—C5 | 1.353 (18) | C39—C40 | 1.3900 |
C4—H4 | 0.9500 | C39—H39 | 0.9500 |
C5—C6 | 1.401 (14) | C40—C41 | 1.3900 |
C5—H5 | 0.9500 | C40—H40 | 0.9500 |
C6—H6 | 0.9500 | C41—C42 | 1.3900 |
C7—C8 | 1.502 (12) | C41—H41 | 0.9500 |
C7—H7A | 0.9900 | C42—N10 | 1.3900 |
C7—H7B | 0.9900 | C42—H42 | 0.9500 |
C8—C9 | 1.388 (13) | C43—C44 | 1.475 (14) |
C9—C10 | 1.377 (15) | C43—H43A | 0.9900 |
C9—H9 | 0.9500 | C43—H43B | 0.9900 |
C10—C11 | 1.370 (17) | C44—C45 | 1.3900 |
C10—H10 | 0.9500 | C44—N11 | 1.3900 |
C11—C12 | 1.391 (15) | C45—C46 | 1.3900 |
C11—H11 | 0.9500 | C45—H45 | 0.9500 |
C12—H12 | 0.9500 | C46—C47 | 1.3900 |
C13—C14 | 1.499 (12) | C46—H46 | 0.9500 |
C13—H13A | 0.9900 | C47—C48 | 1.3900 |
C13—H13B | 0.9900 | C47—H47 | 0.9500 |
C14—C15 | 1.382 (11) | C48—N11 | 1.3900 |
C15—C16 | 1.373 (14) | C48—H48 | 0.9500 |
C15—H15 | 0.9500 | C49—C50 | 1.485 (12) |
C16—C17 | 1.367 (14) | C49—H49A | 0.9900 |
C16—H16 | 0.9500 | C49—H49B | 0.9900 |
C17—C18 | 1.363 (12) | C50—C51 | 1.3900 |
C17—H17 | 0.9500 | C50—N12 | 1.3900 |
C18—H18 | 0.9500 | C51—C52 | 1.3900 |
Cu2—N5 | 2.035 (6) | C51—H51 | 0.9500 |
Cu2—N7 | 2.060 (6) | C52—C53 | 1.3900 |
Cu2—N8 | 2.061 (7) | C52—H52 | 0.9500 |
Cu2—N6 | 2.071 (6) | C53—C54 | 1.3900 |
Cu2—Br2 | 2.3664 (12) | C53—H53 | 0.9500 |
N5—C31 | 1.475 (11) | C54—N12 | 1.3900 |
N5—C19 | 1.482 (11) | C54—H54 | 0.9500 |
N5—C25 | 1.488 (11) | C37A—C38A | 1.45 (2) |
N6—C24 | 1.346 (11) | C37A—H37C | 0.9900 |
N6—C20 | 1.352 (10) | C37A—H37D | 0.9900 |
N7—C26 | 1.320 (11) | C38A—C39A | 1.3900 |
N7—C30 | 1.360 (11) | C38A—N10A | 1.3900 |
N8—C32 | 1.341 (13) | C39A—C40A | 1.3900 |
N8—C36 | 1.339 (11) | C39A—H39A | 0.9500 |
C19—C20 | 1.500 (12) | C40A—C41A | 1.3900 |
C19—H19A | 0.9900 | C40A—H40A | 0.9500 |
C19—H19B | 0.9900 | C41A—C42A | 1.3900 |
C20—C21 | 1.384 (12) | C41A—H41A | 0.9500 |
C21—C22 | 1.395 (14) | C42A—N10A | 1.3900 |
C21—H21 | 0.9500 | C42A—H42A | 0.9500 |
C22—C23 | 1.367 (14) | C43A—C44A | 1.43 (2) |
C22—H22 | 0.9500 | C43A—H43C | 0.9900 |
C23—C24 | 1.377 (12) | C43A—H43D | 0.9900 |
C23—H23 | 0.9500 | C44A—C45A | 1.3900 |
C24—H24 | 0.9500 | C44A—N11A | 1.3900 |
C25—C26 | 1.505 (12) | C45A—C46A | 1.3900 |
C25—H25A | 0.9900 | C45A—H45A | 0.9500 |
C25—H25B | 0.9900 | C46A—C47A | 1.3900 |
C26—C27 | 1.387 (12) | C46A—H46A | 0.9500 |
C27—C28 | 1.390 (15) | C47A—C48A | 1.3900 |
C27—H27 | 0.9500 | C47A—H47A | 0.9500 |
C28—C29 | 1.374 (16) | C48A—N11A | 1.3900 |
C28—H28 | 0.9500 | C48A—H48A | 0.9500 |
C29—C30 | 1.387 (13) | C49A—C50A | 1.49 (2) |
C29—H29 | 0.9500 | C49A—H49C | 0.9900 |
C30—H30 | 0.9500 | C49A—H49D | 0.9900 |
C31—C32 | 1.503 (13) | C50A—C51A | 1.3900 |
C31—H31A | 0.9900 | C50A—N12A | 1.3900 |
C31—H31B | 0.9900 | C51A—C52A | 1.3900 |
C32—C33 | 1.380 (14) | C51A—H51A | 0.9500 |
C33—C34 | 1.39 (2) | C52A—C53A | 1.3900 |
C33—H33 | 0.9500 | C52A—H52A | 0.9500 |
C34—C35 | 1.36 (2) | C53A—C54A | 1.3900 |
C34—H34 | 0.9500 | C53A—H53A | 0.9500 |
C35—C36 | 1.384 (17) | C54A—N12A | 1.3900 |
C35—H35 | 0.9500 | C54A—H54A | 0.9500 |
N3—Cu1—N1 | 81.5 (3) | N11—Cu3—N10 | 126.2 (4) |
N3—Cu1—N4 | 119.7 (3) | N12A—Cu3—N9 | 77.5 (5) |
N1—Cu1—N4 | 80.4 (3) | N11—Cu3—N9 | 82.6 (3) |
N3—Cu1—N2 | 120.1 (3) | N10—Cu3—N9 | 81.3 (3) |
N1—Cu1—N2 | 81.5 (3) | N12A—Cu3—N10A | 113.6 (6) |
N4—Cu1—N2 | 113.3 (3) | N9—Cu3—N10A | 80.5 (4) |
N3—Cu1—Br1 | 98.9 (2) | N12A—Cu3—N11A | 121.0 (8) |
N1—Cu1—Br1 | 179.4 (2) | N9—Cu3—N11A | 79.7 (6) |
N4—Cu1—Br1 | 99.82 (18) | N10A—Cu3—N11A | 115.0 (7) |
N2—Cu1—Br1 | 97.8 (2) | N11—Cu3—N12 | 118.1 (4) |
C7—N1—C13 | 111.9 (6) | N10—Cu3—N12 | 110.5 (4) |
C7—N1—C1 | 112.2 (7) | N9—Cu3—N12 | 83.3 (3) |
C13—N1—C1 | 110.0 (6) | N12A—Cu3—Br3 | 102.8 (5) |
C7—N1—Cu1 | 107.6 (5) | N11—Cu3—Br3 | 97.3 (3) |
C13—N1—Cu1 | 107.1 (5) | N10—Cu3—Br3 | 98.4 (2) |
C1—N1—Cu1 | 107.9 (5) | N9—Cu3—Br3 | 179.7 (2) |
C2—N2—C6 | 119.3 (8) | N10A—Cu3—Br3 | 99.2 (3) |
C2—N2—Cu1 | 114.5 (6) | N11A—Cu3—Br3 | 100.3 (5) |
C6—N2—Cu1 | 126.0 (7) | N12—Cu3—Br3 | 97.0 (2) |
C8—N3—C12 | 119.1 (8) | C43—N9—C37 | 117.6 (8) |
C8—N3—Cu1 | 113.2 (6) | C49A—N9—C43A | 118.1 (12) |
C12—N3—Cu1 | 127.2 (7) | C43—N9—C49 | 111.6 (7) |
C14—N4—C18 | 118.0 (7) | C37—N9—C49 | 108.0 (8) |
C14—N4—Cu1 | 114.7 (5) | C49A—N9—C37A | 107.2 (12) |
C18—N4—Cu1 | 126.8 (5) | C43A—N9—C37A | 99.7 (10) |
N1—C1—C2 | 109.9 (7) | C49A—N9—Cu3 | 114.9 (9) |
N1—C1—H1A | 109.7 | C43—N9—Cu3 | 107.3 (6) |
C2—C1—H1A | 109.7 | C37—N9—Cu3 | 107.8 (5) |
N1—C1—H1B | 109.7 | C43A—N9—Cu3 | 109.9 (8) |
C2—C1—H1B | 109.7 | C49—N9—Cu3 | 103.4 (5) |
H1A—C1—H1B | 108.2 | C37A—N9—Cu3 | 105.0 (7) |
N2—C2—C3 | 121.7 (9) | N9—C37—C38 | 110.6 (8) |
N2—C2—C1 | 115.2 (7) | N9—C37—H37A | 109.5 |
C3—C2—C1 | 123.1 (9) | C38—C37—H37A | 109.5 |
C4—C3—C2 | 118.8 (11) | N9—C37—H37B | 109.5 |
C4—C3—H3 | 120.6 | C38—C37—H37B | 109.5 |
C2—C3—H3 | 120.6 | H37A—C37—H37B | 108.1 |
C5—C4—C3 | 120.3 (10) | C39—C38—N10 | 120.0 |
C5—C4—H4 | 119.9 | C39—C38—C37 | 124.6 (7) |
C3—C4—H4 | 119.9 | N10—C38—C37 | 115.3 (7) |
C4—C5—C6 | 118.5 (10) | C40—C39—C38 | 120.0 |
C4—C5—H5 | 120.7 | C40—C39—H39 | 120.0 |
C6—C5—H5 | 120.7 | C38—C39—H39 | 120.0 |
N2—C6—C5 | 121.3 (10) | C39—C40—C41 | 120.0 |
N2—C6—H6 | 119.3 | C39—C40—H40 | 120.0 |
C5—C6—H6 | 119.3 | C41—C40—H40 | 120.0 |
N1—C7—C8 | 108.6 (7) | C42—C41—C40 | 120.0 |
N1—C7—H7A | 110.0 | C42—C41—H41 | 120.0 |
C8—C7—H7A | 110.0 | C40—C41—H41 | 120.0 |
N1—C7—H7B | 110.0 | N10—C42—C41 | 120.0 |
C8—C7—H7B | 110.0 | N10—C42—H42 | 120.0 |
H7A—C7—H7B | 108.3 | C41—C42—H42 | 120.0 |
N3—C8—C9 | 122.3 (9) | C42—N10—C38 | 120.0 |
N3—C8—C7 | 115.4 (7) | C42—N10—Cu3 | 127.7 (4) |
C9—C8—C7 | 122.2 (8) | C38—N10—Cu3 | 112.1 (4) |
C10—C9—C8 | 118.3 (10) | N9—C43—C44 | 112.2 (8) |
C10—C9—H9 | 120.9 | N9—C43—H43A | 109.2 |
C8—C9—H9 | 120.9 | C44—C43—H43A | 109.2 |
C11—C10—C9 | 119.7 (10) | N9—C43—H43B | 109.2 |
C11—C10—H10 | 120.2 | C44—C43—H43B | 109.2 |
C9—C10—H10 | 120.2 | H43A—C43—H43B | 107.9 |
C10—C11—C12 | 119.8 (10) | C45—C44—N11 | 120.0 |
C10—C11—H11 | 120.1 | C45—C44—C43 | 123.8 (7) |
C12—C11—H11 | 120.1 | N11—C44—C43 | 116.2 (7) |
N3—C12—C11 | 120.8 (10) | C46—C45—C44 | 120.0 |
N3—C12—H12 | 119.6 | C46—C45—H45 | 120.0 |
C11—C12—H12 | 119.6 | C44—C45—H45 | 120.0 |
N1—C13—C14 | 109.4 (6) | C45—C46—C47 | 120.0 |
N1—C13—H13A | 109.8 | C45—C46—H46 | 120.0 |
C14—C13—H13A | 109.8 | C47—C46—H46 | 120.0 |
N1—C13—H13B | 109.8 | C46—C47—C48 | 120.0 |
C14—C13—H13B | 109.8 | C46—C47—H47 | 120.0 |
H13A—C13—H13B | 108.2 | C48—C47—H47 | 120.0 |
N4—C14—C15 | 122.4 (8) | C47—C48—N11 | 120.0 |
N4—C14—C13 | 114.1 (7) | C47—C48—H48 | 120.0 |
C15—C14—C13 | 123.5 (7) | N11—C48—H48 | 120.0 |
C16—C15—C14 | 118.1 (8) | C48—N11—C44 | 120.0 |
C16—C15—H15 | 121.0 | C48—N11—Cu3 | 129.4 (6) |
C14—C15—H15 | 121.0 | C44—N11—Cu3 | 110.6 (6) |
C17—C16—C15 | 120.2 (8) | C50—C49—N9 | 112.4 (7) |
C17—C16—H16 | 119.9 | C50—C49—H49A | 109.1 |
C15—C16—H16 | 119.9 | N9—C49—H49A | 109.1 |
C18—C17—C16 | 118.5 (8) | C50—C49—H49B | 109.1 |
C18—C17—H17 | 120.7 | N9—C49—H49B | 109.1 |
C16—C17—H17 | 120.7 | H49A—C49—H49B | 107.9 |
N4—C18—C17 | 122.7 (8) | C51—C50—N12 | 120.0 |
N4—C18—H18 | 118.7 | C51—C50—C49 | 125.7 (6) |
C17—C18—H18 | 118.7 | N12—C50—C49 | 114.3 (6) |
N5—Cu2—N7 | 81.3 (3) | C52—C51—C50 | 120.0 |
N5—Cu2—N8 | 81.0 (3) | C52—C51—H51 | 120.0 |
N7—Cu2—N8 | 118.7 (3) | C50—C51—H51 | 120.0 |
N5—Cu2—N6 | 81.2 (3) | C51—C52—C53 | 120.0 |
N7—Cu2—N6 | 116.3 (2) | C51—C52—H52 | 120.0 |
N8—Cu2—N6 | 118.1 (2) | C53—C52—H52 | 120.0 |
N5—Cu2—Br2 | 177.8 (2) | C54—C53—C52 | 120.0 |
N7—Cu2—Br2 | 97.18 (19) | C54—C53—H53 | 120.0 |
N8—Cu2—Br2 | 98.5 (2) | C52—C53—H53 | 120.0 |
N6—Cu2—Br2 | 100.86 (19) | N12—C54—C53 | 120.0 |
C31—N5—C19 | 111.0 (7) | N12—C54—H54 | 120.0 |
C31—N5—C25 | 111.6 (7) | C53—C54—H54 | 120.0 |
C19—N5—C25 | 111.9 (7) | C54—N12—C50 | 120.0 |
C31—N5—Cu2 | 107.3 (5) | C54—N12—Cu3 | 128.6 (4) |
C19—N5—Cu2 | 108.3 (5) | C50—N12—Cu3 | 111.2 (4) |
C25—N5—Cu2 | 106.6 (5) | C38A—C37A—N9 | 108.1 (13) |
C24—N6—C20 | 119.2 (7) | C38A—C37A—H37C | 110.1 |
C24—N6—Cu2 | 127.7 (5) | N9—C37A—H37C | 110.1 |
C20—N6—Cu2 | 113.0 (5) | C38A—C37A—H37D | 110.1 |
C26—N7—C30 | 119.4 (7) | N9—C37A—H37D | 110.1 |
C26—N7—Cu2 | 113.1 (5) | H37C—C37A—H37D | 108.4 |
C30—N7—Cu2 | 127.5 (6) | C39A—C38A—N10A | 120.0 |
C32—N8—C36 | 117.7 (8) | C39A—C38A—C37A | 126.4 (11) |
C32—N8—Cu2 | 113.4 (6) | N10A—C38A—C37A | 113.6 (11) |
C36—N8—Cu2 | 128.6 (7) | C38A—C39A—C40A | 120.0 |
N5—C19—C20 | 110.5 (7) | C38A—C39A—H39A | 120.0 |
N5—C19—H19A | 109.5 | C40A—C39A—H39A | 120.0 |
C20—C19—H19A | 109.5 | C41A—C40A—C39A | 120.0 |
N5—C19—H19B | 109.5 | C41A—C40A—H40A | 120.0 |
C20—C19—H19B | 109.5 | C39A—C40A—H40A | 120.0 |
H19A—C19—H19B | 108.1 | C40A—C41A—C42A | 120.0 |
N6—C20—C21 | 121.7 (8) | C40A—C41A—H41A | 120.0 |
N6—C20—C19 | 115.9 (7) | C42A—C41A—H41A | 120.0 |
C21—C20—C19 | 122.4 (8) | N10A—C42A—C41A | 120.0 |
C20—C21—C22 | 117.5 (8) | N10A—C42A—H42A | 120.0 |
C20—C21—H21 | 121.3 | C41A—C42A—H42A | 120.0 |
C22—C21—H21 | 121.3 | C42A—N10A—C38A | 120.0 |
C23—C22—C21 | 121.2 (8) | C42A—N10A—Cu3 | 122.9 (7) |
C23—C22—H22 | 119.4 | C38A—N10A—Cu3 | 116.7 (7) |
C21—C22—H22 | 119.4 | C44A—C43A—N9 | 113.8 (15) |
C22—C23—C24 | 117.9 (9) | C44A—C43A—H43C | 108.8 |
C22—C23—H23 | 121.0 | N9—C43A—H43C | 108.8 |
C24—C23—H23 | 121.0 | C44A—C43A—H43D | 108.8 |
N6—C24—C23 | 122.4 (8) | N9—C43A—H43D | 108.8 |
N6—C24—H24 | 118.8 | H43C—C43A—H43D | 107.7 |
C23—C24—H24 | 118.8 | C45A—C44A—N11A | 120.0 |
N5—C25—C26 | 110.0 (7) | C45A—C44A—C43A | 127.1 (14) |
N5—C25—H25A | 109.7 | N11A—C44A—C43A | 112.6 (14) |
C26—C25—H25A | 109.7 | C44A—C45A—C46A | 120.0 |
N5—C25—H25B | 109.7 | C44A—C45A—H45A | 120.0 |
C26—C25—H25B | 109.7 | C46A—C45A—H45A | 120.0 |
H25A—C25—H25B | 108.2 | C47A—C46A—C45A | 120.0 |
N7—C26—C27 | 122.8 (8) | C47A—C46A—H46A | 120.0 |
N7—C26—C25 | 116.1 (7) | C45A—C46A—H46A | 120.0 |
C27—C26—C25 | 121.0 (8) | C46A—C47A—C48A | 120.0 |
C26—C27—C28 | 118.2 (9) | C46A—C47A—H47A | 120.0 |
C26—C27—H27 | 120.9 | C48A—C47A—H47A | 120.0 |
C28—C27—H27 | 120.9 | N11A—C48A—C47A | 120.0 |
C29—C28—C27 | 119.2 (9) | N11A—C48A—H48A | 120.0 |
C29—C28—H28 | 120.4 | C47A—C48A—H48A | 120.0 |
C27—C28—H28 | 120.4 | C48A—N11A—C44A | 120.0 |
C28—C29—C30 | 119.6 (10) | C48A—N11A—Cu3 | 123.9 (11) |
C28—C29—H29 | 120.2 | C44A—N11A—Cu3 | 115.7 (11) |
C30—C29—H29 | 120.2 | N9—C49A—C50A | 105.6 (14) |
N7—C30—C29 | 120.7 (9) | N9—C49A—H49C | 110.6 |
N7—C30—H30 | 119.6 | C50A—C49A—H49C | 110.6 |
C29—C30—H30 | 119.6 | N9—C49A—H49D | 110.6 |
N5—C31—C32 | 109.1 (7) | C50A—C49A—H49D | 110.6 |
N5—C31—H31A | 109.9 | H49C—C49A—H49D | 108.7 |
C32—C31—H31A | 109.9 | C51A—C50A—N12A | 120.0 |
N5—C31—H31B | 109.9 | C51A—C50A—C49A | 125.5 (12) |
C32—C31—H31B | 109.9 | N12A—C50A—C49A | 114.5 (12) |
H31A—C31—H31B | 108.3 | C52A—C51A—C50A | 120.0 |
N8—C32—C33 | 123.8 (10) | C52A—C51A—H51A | 120.0 |
N8—C32—C31 | 114.6 (7) | C50A—C51A—H51A | 120.0 |
C33—C32—C31 | 121.4 (10) | C51A—C52A—C53A | 120.0 |
C32—C33—C34 | 117.5 (14) | C51A—C52A—H52A | 120.0 |
C32—C33—H33 | 121.2 | C53A—C52A—H52A | 120.0 |
C34—C33—H33 | 121.2 | C54A—C53A—C52A | 120.0 |
C35—C34—C33 | 119.0 (12) | C54A—C53A—H53A | 120.0 |
C35—C34—H34 | 120.5 | C52A—C53A—H53A | 120.0 |
C33—C34—H34 | 120.5 | C53A—C54A—N12A | 120.0 |
C34—C35—C36 | 120.1 (11) | C53A—C54A—H54A | 120.0 |
C34—C35—H35 | 120.0 | N12A—C54A—H54A | 120.0 |
C36—C35—H35 | 120.0 | C54A—N12A—C50A | 120.0 |
N8—C36—C35 | 121.8 (12) | C54A—N12A—Cu3 | 125.2 (8) |
N8—C36—H36 | 119.1 | C50A—N12A—Cu3 | 114.4 (8) |
C35—C36—H36 | 119.1 | ||
C7—N1—C1—C2 | 82.6 (8) | C43—N9—C37—C38 | 82.4 (10) |
C13—N1—C1—C2 | −152.2 (7) | C49—N9—C37—C38 | −150.2 (8) |
Cu1—N1—C1—C2 | −35.7 (8) | Cu3—N9—C37—C38 | −39.0 (9) |
C6—N2—C2—C3 | −2.4 (14) | N9—C37—C38—C39 | −151.0 (7) |
Cu1—N2—C2—C3 | 173.7 (7) | N9—C37—C38—N10 | 31.9 (10) |
C6—N2—C2—C1 | 176.4 (8) | N10—C38—C39—C40 | 0.0 |
Cu1—N2—C2—C1 | −7.5 (10) | C37—C38—C39—C40 | −177.1 (10) |
N1—C1—C2—N2 | 29.3 (10) | C38—C39—C40—C41 | 0.0 |
N1—C1—C2—C3 | −151.9 (9) | C39—C40—C41—C42 | 0.0 |
N2—C2—C3—C4 | 1.3 (16) | C40—C41—C42—N10 | 0.0 |
C1—C2—C3—C4 | −177.3 (10) | C41—C42—N10—C38 | 0.0 |
C2—C3—C4—C5 | 1.3 (19) | C41—C42—N10—Cu3 | −173.6 (6) |
C3—C4—C5—C6 | −2.9 (19) | C39—C38—N10—C42 | 0.0 |
C2—N2—C6—C5 | 0.7 (14) | C37—C38—N10—C42 | 177.3 (9) |
Cu1—N2—C6—C5 | −174.8 (8) | C39—C38—N10—Cu3 | 174.5 (6) |
C4—C5—C6—N2 | 1.9 (17) | C37—C38—N10—Cu3 | −8.2 (8) |
C13—N1—C7—C8 | 78.2 (8) | C37—N9—C43—C44 | −157.2 (8) |
C1—N1—C7—C8 | −157.7 (7) | C49—N9—C43—C44 | 77.1 (10) |
Cu1—N1—C7—C8 | −39.2 (7) | Cu3—N9—C43—C44 | −35.5 (9) |
C12—N3—C8—C9 | −2.6 (12) | N9—C43—C44—C45 | −155.1 (7) |
Cu1—N3—C8—C9 | 170.0 (7) | N9—C43—C44—N11 | 25.2 (11) |
C12—N3—C8—C7 | 174.6 (8) | N11—C44—C45—C46 | 0.0 |
Cu1—N3—C8—C7 | −12.8 (9) | C43—C44—C45—C46 | −179.7 (10) |
N1—C7—C8—N3 | 35.4 (10) | C44—C45—C46—C47 | 0.0 |
N1—C7—C8—C9 | −147.4 (8) | C45—C46—C47—C48 | 0.0 |
N3—C8—C9—C10 | 1.7 (14) | C46—C47—C48—N11 | 0.0 |
C7—C8—C9—C10 | −175.3 (9) | C47—C48—N11—C44 | 0.0 |
C8—C9—C10—C11 | 0.7 (15) | C47—C48—N11—Cu3 | −179.6 (8) |
C9—C10—C11—C12 | −2.1 (16) | C45—C44—N11—C48 | 0.0 |
C8—N3—C12—C11 | 1.1 (13) | C43—C44—N11—C48 | 179.7 (9) |
Cu1—N3—C12—C11 | −170.4 (7) | C45—C44—N11—Cu3 | 179.7 (7) |
C10—C11—C12—N3 | 1.3 (15) | C43—C44—N11—Cu3 | −0.6 (8) |
C7—N1—C13—C14 | −158.3 (6) | C43—N9—C49—C50 | −157.5 (9) |
C1—N1—C13—C14 | 76.3 (8) | C37—N9—C49—C50 | 71.7 (10) |
Cu1—N1—C13—C14 | −40.7 (7) | Cu3—N9—C49—C50 | −42.4 (9) |
C18—N4—C14—C15 | −1.3 (11) | N9—C49—C50—C51 | −148.6 (7) |
Cu1—N4—C14—C15 | 170.7 (6) | N9—C49—C50—N12 | 33.5 (11) |
C18—N4—C14—C13 | 178.4 (7) | N12—C50—C51—C52 | 0.0 |
Cu1—N4—C14—C13 | −9.6 (8) | C49—C50—C51—C52 | −177.8 (10) |
N1—C13—C14—N4 | 33.9 (9) | C50—C51—C52—C53 | 0.0 |
N1—C13—C14—C15 | −146.4 (8) | C51—C52—C53—C54 | 0.0 |
N4—C14—C15—C16 | −2.0 (13) | C52—C53—C54—N12 | 0.0 |
C13—C14—C15—C16 | 178.3 (8) | C53—C54—N12—C50 | 0.0 |
C14—C15—C16—C17 | 3.4 (13) | C53—C54—N12—Cu3 | −174.5 (7) |
C15—C16—C17—C18 | −1.5 (13) | C51—C50—N12—C54 | 0.0 |
C14—N4—C18—C17 | 3.4 (11) | C49—C50—N12—C54 | 178.1 (9) |
Cu1—N4—C18—C17 | −167.5 (6) | C51—C50—N12—Cu3 | 175.4 (6) |
C16—C17—C18—N4 | −2.0 (12) | C49—C50—N12—Cu3 | −6.5 (8) |
C31—N5—C19—C20 | −81.9 (9) | C49A—N9—C37A—C38A | −79.5 (16) |
C25—N5—C19—C20 | 152.8 (7) | C43A—N9—C37A—C38A | 157.0 (13) |
Cu2—N5—C19—C20 | 35.6 (8) | Cu3—N9—C37A—C38A | 43.1 (14) |
C24—N6—C20—C21 | 1.3 (12) | N9—C37A—C38A—C39A | 147.6 (10) |
Cu2—N6—C20—C21 | 178.7 (6) | N9—C37A—C38A—N10A | −33.2 (16) |
C24—N6—C20—C19 | −176.9 (7) | N10A—C38A—C39A—C40A | 0.0 |
Cu2—N6—C20—C19 | 0.5 (9) | C37A—C38A—C39A—C40A | 179.2 (17) |
N5—C19—C20—N6 | −24.3 (10) | C38A—C39A—C40A—C41A | 0.0 |
N5—C19—C20—C21 | 157.6 (7) | C39A—C40A—C41A—C42A | 0.0 |
N6—C20—C21—C22 | −2.3 (12) | C40A—C41A—C42A—N10A | 0.0 |
C19—C20—C21—C22 | 175.8 (8) | C41A—C42A—N10A—C38A | 0.0 |
C20—C21—C22—C23 | 1.7 (14) | C41A—C42A—N10A—Cu3 | 172.1 (10) |
C21—C22—C23—C24 | −0.2 (14) | C39A—C38A—N10A—C42A | 0.0 |
C20—N6—C24—C23 | 0.3 (12) | C37A—C38A—N10A—C42A | −179.3 (15) |
Cu2—N6—C24—C23 | −176.6 (6) | C39A—C38A—N10A—Cu3 | −172.6 (9) |
C22—C23—C24—N6 | −0.9 (14) | C37A—C38A—N10A—Cu3 | 8.2 (13) |
C31—N5—C25—C26 | 154.8 (7) | C49A—N9—C43A—C44A | 166.1 (15) |
C19—N5—C25—C26 | −80.3 (8) | C37A—N9—C43A—C44A | −78.4 (16) |
Cu2—N5—C25—C26 | 37.9 (8) | Cu3—N9—C43A—C44A | 31.6 (17) |
C30—N7—C26—C27 | −2.6 (12) | N9—C43A—C44A—C45A | 157.4 (13) |
Cu2—N7—C26—C27 | 176.1 (7) | N9—C43A—C44A—N11A | −28.8 (19) |
C30—N7—C26—C25 | −178.6 (7) | N11A—C44A—C45A—C46A | 0.0 |
Cu2—N7—C26—C25 | 0.2 (9) | C43A—C44A—C45A—C46A | 173 (2) |
N5—C25—C26—N7 | −26.0 (10) | C44A—C45A—C46A—C47A | 0.0 |
N5—C25—C26—C27 | 158.0 (8) | C45A—C46A—C47A—C48A | 0.0 |
N7—C26—C27—C28 | 2.9 (14) | C46A—C47A—C48A—N11A | 0.0 |
C25—C26—C27—C28 | 178.6 (9) | C47A—C48A—N11A—C44A | 0.0 |
C26—C27—C28—C29 | −2.3 (15) | C47A—C48A—N11A—Cu3 | 172.5 (15) |
C27—C28—C29—C30 | 1.6 (15) | C45A—C44A—N11A—C48A | 0.0 |
C26—N7—C30—C29 | 1.8 (12) | C43A—C44A—N11A—C48A | −174.3 (19) |
Cu2—N7—C30—C29 | −176.7 (7) | C45A—C44A—N11A—Cu3 | −173.1 (14) |
C28—C29—C30—N7 | −1.3 (14) | C43A—C44A—N11A—Cu3 | 12.6 (16) |
C19—N5—C31—C32 | 159.0 (8) | C43A—N9—C49A—C50A | −92.7 (16) |
C25—N5—C31—C32 | −75.6 (9) | C37A—N9—C49A—C50A | 155.9 (13) |
Cu2—N5—C31—C32 | 40.8 (9) | Cu3—N9—C49A—C50A | 39.6 (16) |
C36—N8—C32—C33 | −0.7 (14) | N9—C49A—C50A—C51A | 151.3 (12) |
Cu2—N8—C32—C33 | −174.8 (10) | N9—C49A—C50A—N12A | −31.7 (18) |
C36—N8—C32—C31 | −176.3 (8) | N12A—C50A—C51A—C52A | 0.0 |
Cu2—N8—C32—C31 | 9.6 (10) | C49A—C50A—C51A—C52A | 176.9 (18) |
N5—C31—C32—N8 | −34.0 (11) | C50A—C51A—C52A—C53A | 0.0 |
N5—C31—C32—C33 | 150.3 (11) | C51A—C52A—C53A—C54A | 0.0 |
N8—C32—C33—C34 | 1 (2) | C52A—C53A—C54A—N12A | 0.0 |
C31—C32—C33—C34 | 176.8 (13) | C53A—C54A—N12A—C50A | 0.0 |
C32—C33—C34—C35 | −1 (2) | C53A—C54A—N12A—Cu3 | 172.3 (13) |
C33—C34—C35—C36 | 0 (2) | C51A—C50A—N12A—C54A | 0.0 |
C32—N8—C36—C35 | −0.6 (13) | C49A—C50A—N12A—C54A | −177.2 (16) |
Cu2—N8—C36—C35 | 172.4 (8) | C51A—C50A—N12A—Cu3 | −173.1 (12) |
C34—C35—C36—N8 | 1.1 (18) | C49A—C50A—N12A—Cu3 | 9.7 (15) |
Acknowledgements
The authors would like to thank all students who participated in this laboratory experiment for their contribution and the University of Notre Dame for instrument support.
References
Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science Google Scholar
Britovsek, G. P., England, J. & White, A. P. (2005). Inorg. Chem. 44, 8125–8134. Web of Science CSD CrossRef PubMed CAS Google Scholar
Bruker (2015). APEX3, SAINT, SADABS and XP. Bruker–Nonius AXS Inc. Madison, Wisconsin, USA. Google Scholar
Bruno, I. J., Cole, J. C., Kessler, M., Luo, J., Motherwell, W. D. S., Purkis, L. H., Smith, B. R., Taylor, R., Cooper, R. I., Harris, S. E. & Orpen, A. G. (2004). J. Chem. Inf. Comput. Sci. 44, 2133–2144. Web of Science CSD CrossRef PubMed CAS Google Scholar
Eckenhoff, W. T., Garrity, S. T. & Pintauer, T. (2008). Eur. J. Inorg. Chem. pp. 563–571. Web of Science CSD CrossRef Google Scholar
Eckenhoff, W. T. & Pintauer, T. (2010). Catal. Rev. 52, 1–59. Web of Science CrossRef CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
He, Z., Chaimungkalanont, P., Craig, D. C. & Colbran, S. B. (2000). J. Chem. Soc. Dalton Trans. pp. 1419–1429. Web of Science CSD CrossRef Google Scholar
Iqbal, J., Bhatia, B. & Nayyar, N. K. (1994). Chem. Rev. 94, 519–564. CrossRef CAS Web of Science Google Scholar
Kaur, A., Ribelli, T. G., Schröder, K., Matyjaszewski, K. & Pintauer, T. (2015). Inorg. Chem. 54, 1474–1486. Web of Science CSD CrossRef CAS PubMed Google Scholar
Kharasch, M. S., Jensen, E. V. & Urry, W. H. (1945). Science, 102, 128–129. CrossRef PubMed CAS Web of Science Google Scholar
Maiti, D., Woertink, J. S., Vance, M. A., Milligan, A. E., Narducci Sarjeant, A. A., Solomon, E. I. & Karlin, K. D. (2007). J. Am. Chem. Soc. 129, 8882–8892. Web of Science CSD CrossRef PubMed CAS Google Scholar
Matyjaszewski, K., Göbelt, B., Paik, H. & Horwitz, C. (2001). Macromolecules, 34, 430–440. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Tang, W., Kwak, Y., Braunecker, W., Tsarevsky, N. V., Coote, M. L. & Matyjaszewski, K. (2008). J. Am. Chem. Soc. 130, 10702–10713. Web of Science CrossRef PubMed CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.