research communications
{1,1′-Bis[(pyridin-2-yl)methyl]-2,2′-bipiperidyl}(perchlorato)copper(II) perchlorate
aDepartment of Chemistry, Tufts University, Medford, Massachusetts 02155, USA, and bBruker AXS Inc., 5465 E. Cheryl Parkway, Madison, WI 53711, USA
*Correspondence e-mail: elena.rybak-akimova@tufts.edu
The title complex, [CuII(ClO4)(mesoPYBP)](ClO4) {PYBP = 1,1′-bis[(pyridin-2-yl)methyl]-2,2′-bipiperidyl, C22H30N4}, was prepared and found to crystallize with two crystallographically independent complex salt moieties. The metal atoms of the cations adopt a pseudo-square-pyramidal coordination geometry, where the tetradentate aminopyridine ligands (PYBP) are wrapped around the Cu atoms in the equatorial plane. The Cu—O bonds involving an O atom of the coordinating perchlorate anion are approximately perpendicular to the plane. The two remaining non-coordinating perchlorate anions are involved in several C—H⋯O hydrogen bonds with the PYBP ligand and balance the total charge of the complex salt. The two crystallographically independent moieties are related to each other via a pseudo-translation along the a-axis direction. Exact translational symmetry is broken by (i) a difference in the conformation of one of the piperidine rings, featuring a chair conformation in one of the cations, and a sterically disfavored boat conformation in the other; and (ii) by modulation of the non-coordinating perchlorate anions.
Keywords: crystal structure; copper(II) complex; aminopyridine.
CCDC reference: 1558167
1. Chemical context
The design and synthesis of a family of linear tetradentate aminopyridine ligands, featuring a diamine derivative backbone (e.g. 1,2-cyclohexyldiamine or 2,2′-dipyrrolidyl) and two picolyl arms attached to the amine nitrogen atoms, have frequently been discussed (Murphy & Stack, 2006; Yazerski et al., 2014). Common examples of linear tetradentate aminopyridine ligands are shown in Fig. 1. The Fe and Mn complexes bearing this type of ligand show good for olefin epoxidation (Lyakin et al., 2012; Mikhalyova et al., 2012), as well as aromatic (Makhlynets & Rybak-Akimova, 2010) and aliphatic (Ottenbacher et al., 2015) C—H activation. Related copper(II) complexes with aminopyridine ligands have also been synthesized and characterized (Singh et al., 2017; Kani et al., 2000; Liebov et al., 2011). Potential applications of these complexes include fluorescent sensing of NO. The copper(II) ion in complexes with an appended fluorophore is readily reduced by nitric oxide with concomitant fluorescence enhancement (Kumar et al. 2013a,b).
2. Structural commentary
The title compound crystallizes with two crystallographically independent moieties, consisting of a [CuII(ClO4)(mesoPYBP)] {PYBP = 1,1′-bis[(pyridin-2-yl)methyl]-2,2′-bipiperidyl} cation and another non-coordinating ClO4− anion [PYBP = N,N′-di-(2-picolyl)-2,2′-dipiperidyl]. Like some other CuII aminopyridine complexes (Singh et al., 2017; Kani et al., 2000; Liebov et al., 2011), the cationic complex consists of a five-coordinate Cu ion in a distorted square-pyramidal geometry.
The tetradentate mesoPYBP ligand surrounds the metal ion in the basal plane (Fig. 2). One of the two remaining octahedral sites is occupied by the oxygen atom of a coordinating perchlorate anion, while the other site remains vacant. Another perchlorate anion in the outer sphere balances the net charge and connects nearby complex cations via C—H⋯O hydrogen bonds. The two chemically equivalent moieties are related to each other via a pseudo-translation by half a along the a-axis direction (Fig. 3). Similar to recently discussed crystal structures of Cu–N2/Py2 complexes (Singh, et al. 2017), the exact translational symmetry is broken by slightly different conformations of the two complex cations.
As shown in Fig. 3, one of the cations (the red Cu1 moiety) has both piperidine rings in a chair conformation, while the other complex cation (the green Cu2 moiety) has one piperidine ring in a sterically disfavored boat conformation (shown in light green). The reason the second cation adopts this unfavorable conformation can be tentatively traced back to the packing interactions of the cations and perchlorate anions. The non-coordinating perchlorate anions (shown in light red/green) are modulated along the direction of the pseudo-translation, allowing for the formation of more favorable C—H⋯O interactions between the C—H units of the pyridyl segments and the perchlorate oxygen atoms (see Supramolecular features section), thus leading to a more favorable packing of the structure as a whole. As a result of the different conformations in the two complex cations, the Cu2—Nbp bonds [2.0226 (16) and 2.0078 (16) Å] differ by 0.015 Å, but the Cu2—Npy bonds [1.9901 (16) and 1.9890 (16) Å] are similar. In contrast, the piperidine rings of the other molecule (Cu1 moiety) are both in the more favorable chair conformation; the Cu1—Nbp distances [2.0349 (16) and 2.0365 (16) Å] are similar, but the Cu1—Npy distances [1.9808 (16) and 2.0309 (16) Å] differ. These Cu—N distances fall into the range of some other CuII aminopyridine complexes (1.98– 2.03 Å; Singh et al., 2017; Kani et al., 2000; Liebov et al., 2011). The metal-coordinating perchlorate ions are only weakly bound, as expected for a d9 copper(II) complex, with Cu1—O and Cu2—O distances of 2.2038 (14) and 2.3438 (15) Å, respectively.
3. Supramolecular features
Details of hydrogen-bonding parameters are listed in Table 1. There are in total twelve C—H⋯O hydrogen bonds, between aromatic and aliphatic C—H units and perchlorate O atoms (Fig. 4). Among these hydrogen bonds, only three involve the inner-sphere perchlorato ligand (C6—H6A⋯O3ii; C17—H17B⋯O4ii; C28—H28B⋯O12iv); all of these hydrogen bonds are intermolecular, linking with the hydrogen atoms on the pyridine α-carbons of the adjacent Cu-mesoPYBP cations. The perchlorate close to the Cu1 moiety forms six hydrogen bonds with four adjacent complex cations (both Cu1 and Cu2), while that close to the Cu2 moiety only forms three hydrogen bonds with two adjacent complex cations (Cu2 only). This difference in hydrogen-bonding environments of the two outer-sphere perchlorates breaks the symmetry between them and between the cation moieties. All C⋯O distances of the C—H⋯O interactions (3.08–3.29 Å) are roughly equal to or shorter than the sum of van der Waals radii of the corresponding atoms (3.25 Å), indicating normal strength interactions.
4. Synthesis and crystallization
The synthesis of the mesoPYBP ligand involves two steps. A detailed synthetic procedure for (2R,2′S)-2,2′-bipiperidine-1,1′-diium dibromide (mesoBP·2HBr) via reductive hydrogenation of 2,2′-dipyridyl was reported by Herrmann et al. (2006) and Yang et al. (2013). 1.81 g mesoBP·2HBr was dissolved in 8 mL H2O, and 8 mL of 5 M NaOH solution was added, followed by addition of 10 mL of CH2Cl2. With vigorous stirring, 4 mL of an aqueous solution containing 1.86 g picolyl chloride hydrochloride was added dropwise, and the reaction mixture was stirred for about four days. The two layers were separated, and the aqueous layer was extracted with CH2Cl2. The organic layers were combined and the solvent was evaporated under vacuum. The ligand was purified by adding concentrated HBr and subsequent recrystallization from EtOH. 1H NMR (CDCl3): 8.60 (d, 2H); 8.24 (t, 2H); 7.80 (d, 2H); 7.73 (t, 2H); 4.25 (d, 2H); 3.55 (s, 2H); 3.07 (d, 2H); 2.84 (s, 2H); 2.05 (d, 2H); 1.78 (m, 4H); 1.66 (m, 4H); 1.51 (m, 2H). 13C NMR (CDCl3): 161.3; 149.0; 136.5; 122.5; 121.6; 63.8; 60.3; 54.2; 27.7; 24.9; 24.8. The mesoPYBP·xHBr was basified with excess NaOH in aqueous solution, and extracted with CH2Cl2. The CH2Cl2 solution was dried over MgSO4 and solvents were removed by rotary evaporation, giving mesoPYBP as a colorless oil (yield: 1.47g, 76%).
Under ambient atmosphere, 0.70 g (2 mmol) mesoPYBP ligand was dissolved in 2 mL MeCN. 0.74 g (2 mmol) Cu(ClO4)2·6H2O (MW = 370.54g mol−1) was dissolved in minimal MeCN. The solutions were combined and stirred for two days; any precipitate was removed by filtration and discarded. 1.22 g (85%) [CuII(mesoPYBP)(ClO4)](ClO4) was obtained as dark-blue crystals by slow evaporation of the MeCN solution. The crystals decomposed and became black within 15 minutes at 503 K (caution: heating perchlorate-containing compounds may lead to explosion). UV–Vis λmax: 625 nm (molar absorptivity: 0.59 L mol−1 cm−1). IR (in KBr pellet) νmax: 3071, 2958, 1610, 1444, 1081, 1025, 780 cm−1.
5. details
Crystal data, data collection and structure . H atoms were placed at calculated geometries and allowed to ride on their parent C atoms. The C—H distances were set to 0.99 Å for CH2, 1.00 Å for CH and 0.95 Å for aromatic CH bonds. Isotropic displacement parameters were set to 1.2 times of the equivalent isotropic displacement parameter of the parent atom.
details are summarized in Table 2
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Supporting information
CCDC reference: 1558167
https://doi.org/10.1107/S2056989017009410/zl2706sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017009410/zl2706Isup2.hkl
Data collection: APEX2 (Bruker, 2013); cell
SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2006) and OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).[Cu(ClO4)(C22H30N4)]ClO4 | F(000) = 2536 |
Mr = 612.94 | Dx = 1.653 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 18.4079 (7) Å | Cell parameters from 9672 reflections |
b = 14.0001 (5) Å | θ = 2.9–28.6° |
c = 19.9387 (7) Å | µ = 1.16 mm−1 |
β = 106.531 (1)° | T = 100 K |
V = 4926.1 (3) Å3 | Block, clear dark blue |
Z = 8 | 0.26 × 0.17 × 0.17 mm |
Bruker APEXII CCD diffractometer | 12921 independent reflections |
Radiation source: sealed tube | 9894 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.062 |
φ and ω scans | θmax = 28.9°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −24→25 |
Tmin = 0.752, Tmax = 0.832 | k = −19→19 |
144743 measured reflections | l = −26→27 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0444P)2 + 3.2192P] where P = (Fo2 + 2Fc2)/3 |
12921 reflections | (Δ/σ)max = 0.001 |
667 parameters | Δρmax = 0.73 e Å−3 |
0 restraints | Δρmin = −0.33 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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.02444 (2) | 0.68277 (2) | 0.31076 (2) | 0.00959 (6) | |
Cl1 | 0.08984 (3) | 0.45819 (3) | 0.32748 (2) | 0.01394 (10) | |
O1 | 0.10311 (8) | 0.56114 (10) | 0.32272 (8) | 0.0177 (3) | |
O2 | 0.05659 (10) | 0.44218 (12) | 0.38324 (9) | 0.0306 (4) | |
O3 | 0.16136 (9) | 0.41064 (11) | 0.34111 (9) | 0.0253 (4) | |
O4 | 0.03949 (9) | 0.42629 (11) | 0.26271 (8) | 0.0255 (4) | |
N1 | −0.03644 (9) | 0.65169 (12) | 0.21421 (8) | 0.0121 (3) | |
N2 | −0.07905 (9) | 0.68126 (11) | 0.32858 (8) | 0.0105 (3) | |
N3 | 0.06521 (9) | 0.74269 (11) | 0.40726 (8) | 0.0102 (3) | |
N4 | 0.10057 (9) | 0.77156 (11) | 0.28661 (8) | 0.0109 (3) | |
C1 | −0.01454 (11) | 0.60979 (14) | 0.16256 (10) | 0.0143 (4) | |
H1 | 0.0359 | 0.5867 | 0.1720 | 0.017* | |
C2 | −0.06345 (12) | 0.59934 (14) | 0.09607 (10) | 0.0158 (4) | |
H2 | −0.0465 | 0.5708 | 0.0600 | 0.019* | |
C3 | −0.13776 (12) | 0.63123 (15) | 0.08274 (11) | 0.0163 (4) | |
H3 | −0.1724 | 0.6244 | 0.0375 | 0.020* | |
C4 | −0.16070 (12) | 0.67310 (14) | 0.13633 (10) | 0.0142 (4) | |
H4 | −0.2113 | 0.6951 | 0.1285 | 0.017* | |
C5 | −0.10869 (11) | 0.68225 (14) | 0.20133 (10) | 0.0128 (4) | |
C6 | −0.12721 (11) | 0.72662 (14) | 0.26330 (10) | 0.0131 (4) | |
H6A | −0.1174 | 0.7962 | 0.2644 | 0.016* | |
H6B | −0.1814 | 0.7167 | 0.2597 | 0.016* | |
C7 | −0.10848 (11) | 0.58239 (14) | 0.33443 (10) | 0.0126 (4) | |
H7A | −0.0695 | 0.5459 | 0.3695 | 0.015* | |
H7B | −0.1173 | 0.5495 | 0.2888 | 0.015* | |
C8 | −0.18186 (11) | 0.58191 (15) | 0.35551 (11) | 0.0168 (4) | |
H8A | −0.2221 | 0.6152 | 0.3195 | 0.020* | |
H8B | −0.1984 | 0.5153 | 0.3589 | 0.020* | |
C9 | −0.16941 (12) | 0.63173 (16) | 0.42585 (11) | 0.0185 (4) | |
H9A | −0.1317 | 0.5957 | 0.4625 | 0.022* | |
H9B | −0.2176 | 0.6333 | 0.4387 | 0.022* | |
C10 | −0.14101 (11) | 0.73401 (15) | 0.42194 (11) | 0.0169 (4) | |
H10A | −0.1262 | 0.7613 | 0.4697 | 0.020* | |
H10B | −0.1836 | 0.7728 | 0.3933 | 0.020* | |
C11 | −0.07351 (11) | 0.74408 (14) | 0.39108 (10) | 0.0116 (4) | |
H11 | −0.0760 | 0.8111 | 0.3732 | 0.014* | |
C12 | 0.00505 (11) | 0.73466 (14) | 0.44545 (10) | 0.0116 (4) | |
H12 | 0.0113 | 0.7911 | 0.4773 | 0.014* | |
C13 | 0.01545 (11) | 0.64557 (15) | 0.49124 (10) | 0.0155 (4) | |
H13A | −0.0211 | 0.6475 | 0.5192 | 0.019* | |
H13B | 0.0040 | 0.5884 | 0.4608 | 0.019* | |
C14 | 0.09498 (12) | 0.63660 (15) | 0.54021 (11) | 0.0176 (4) | |
H14A | 0.0987 | 0.5794 | 0.5702 | 0.021* | |
H14B | 0.1076 | 0.6936 | 0.5708 | 0.021* | |
C15 | 0.14985 (12) | 0.62794 (15) | 0.49577 (11) | 0.0183 (4) | |
H15A | 0.2023 | 0.6209 | 0.5264 | 0.022* | |
H15B | 0.1373 | 0.5708 | 0.4654 | 0.022* | |
C16 | 0.14381 (11) | 0.71641 (15) | 0.45137 (11) | 0.0160 (4) | |
H16A | 0.1763 | 0.7076 | 0.4199 | 0.019* | |
H16B | 0.1646 | 0.7709 | 0.4826 | 0.019* | |
C17 | 0.07262 (11) | 0.84384 (13) | 0.38524 (10) | 0.0114 (4) | |
H17A | 0.0984 | 0.8830 | 0.4265 | 0.014* | |
H17B | 0.0218 | 0.8714 | 0.3637 | 0.014* | |
C18 | 0.11812 (11) | 0.84388 (14) | 0.33317 (10) | 0.0116 (4) | |
C19 | 0.17292 (11) | 0.91093 (14) | 0.33209 (10) | 0.0138 (4) | |
H19 | 0.1857 | 0.9597 | 0.3666 | 0.017* | |
C20 | 0.20890 (11) | 0.90567 (14) | 0.27970 (10) | 0.0142 (4) | |
H20 | 0.2469 | 0.9507 | 0.2779 | 0.017* | |
C21 | 0.18860 (11) | 0.83379 (14) | 0.23020 (10) | 0.0136 (4) | |
H21 | 0.2110 | 0.8304 | 0.1928 | 0.016* | |
C22 | 0.13520 (11) | 0.76678 (14) | 0.23583 (10) | 0.0133 (4) | |
H22 | 0.1228 | 0.7161 | 0.2029 | 0.016* | |
Cu2 | 0.49341 (2) | 0.17766 (2) | 0.19964 (2) | 0.01095 (6) | |
Cl3 | 0.41163 (3) | −0.05475 (3) | 0.18440 (3) | 0.01515 (10) | |
O9 | 0.41362 (9) | 0.04702 (10) | 0.19910 (8) | 0.0223 (3) | |
O10 | 0.44337 (11) | −0.07054 (13) | 0.12767 (10) | 0.0412 (5) | |
O11 | 0.33464 (9) | −0.08692 (11) | 0.16571 (9) | 0.0275 (4) | |
O12 | 0.45447 (10) | −0.10456 (12) | 0.24556 (9) | 0.0360 (4) | |
N5 | 0.40939 (9) | 0.25668 (11) | 0.21435 (8) | 0.0115 (3) | |
N6 | 0.45302 (9) | 0.22413 (12) | 0.09988 (8) | 0.0126 (3) | |
N7 | 0.59457 (9) | 0.16475 (11) | 0.18103 (8) | 0.0108 (3) | |
N8 | 0.55271 (9) | 0.14352 (12) | 0.29660 (9) | 0.0140 (3) | |
C23 | 0.37548 (11) | 0.25160 (15) | 0.26563 (10) | 0.0146 (4) | |
H23 | 0.3914 | 0.2041 | 0.3008 | 0.018* | |
C24 | 0.31802 (11) | 0.31360 (15) | 0.26878 (11) | 0.0168 (4) | |
H24 | 0.2957 | 0.3097 | 0.3062 | 0.020* | |
C25 | 0.29354 (11) | 0.38124 (15) | 0.21670 (11) | 0.0183 (4) | |
H25 | 0.2537 | 0.4239 | 0.2175 | 0.022* | |
C26 | 0.32803 (11) | 0.38601 (15) | 0.16321 (11) | 0.0165 (4) | |
H26 | 0.3118 | 0.4315 | 0.1267 | 0.020* | |
C27 | 0.38641 (11) | 0.32336 (14) | 0.16405 (10) | 0.0131 (4) | |
C28 | 0.42904 (12) | 0.32362 (14) | 0.10987 (10) | 0.0141 (4) | |
H28A | 0.3962 | 0.3488 | 0.0651 | 0.017* | |
H28B | 0.4741 | 0.3654 | 0.1254 | 0.017* | |
C29 | 0.38561 (12) | 0.16527 (15) | 0.06126 (11) | 0.0187 (4) | |
H29A | 0.3429 | 0.1786 | 0.0809 | 0.022* | |
H29B | 0.3985 | 0.0967 | 0.0688 | 0.022* | |
C30 | 0.36060 (13) | 0.18549 (16) | −0.01677 (11) | 0.0213 (5) | |
H30A | 0.3442 | 0.2529 | −0.0249 | 0.026* | |
H30B | 0.3169 | 0.1443 | −0.0397 | 0.026* | |
C31 | 0.42578 (13) | 0.16654 (17) | −0.04895 (11) | 0.0239 (5) | |
H31A | 0.4127 | 0.1111 | −0.0810 | 0.029* | |
H31B | 0.4322 | 0.2228 | −0.0768 | 0.029* | |
C32 | 0.50065 (12) | 0.14641 (16) | 0.00728 (11) | 0.0194 (4) | |
H32A | 0.4982 | 0.0833 | 0.0289 | 0.023* | |
H32B | 0.5429 | 0.1452 | −0.0143 | 0.023* | |
C33 | 0.51477 (12) | 0.22413 (14) | 0.06317 (10) | 0.0145 (4) | |
H33 | 0.5098 | 0.2863 | 0.0375 | 0.017* | |
C34 | 0.59262 (11) | 0.22733 (14) | 0.11918 (10) | 0.0134 (4) | |
H34 | 0.5980 | 0.2942 | 0.1376 | 0.016* | |
C35 | 0.66139 (12) | 0.21106 (15) | 0.09117 (11) | 0.0178 (4) | |
H35A | 0.6515 | 0.2426 | 0.0450 | 0.021* | |
H35B | 0.7061 | 0.2424 | 0.1233 | 0.021* | |
C36 | 0.68059 (12) | 0.10575 (15) | 0.08316 (11) | 0.0181 (4) | |
H36A | 0.6412 | 0.0771 | 0.0437 | 0.022* | |
H36B | 0.7297 | 0.1014 | 0.0723 | 0.022* | |
C37 | 0.68517 (11) | 0.05028 (15) | 0.14978 (11) | 0.0165 (4) | |
H37A | 0.7285 | 0.0738 | 0.1880 | 0.020* | |
H37B | 0.6936 | −0.0183 | 0.1423 | 0.020* | |
C38 | 0.61207 (11) | 0.06226 (13) | 0.17035 (10) | 0.0126 (4) | |
H38A | 0.5696 | 0.0344 | 0.1333 | 0.015* | |
H38B | 0.6164 | 0.0264 | 0.2141 | 0.015* | |
C39 | 0.64847 (11) | 0.20258 (14) | 0.24607 (10) | 0.0143 (4) | |
H39A | 0.6474 | 0.2733 | 0.2454 | 0.017* | |
H39B | 0.7006 | 0.1816 | 0.2488 | 0.017* | |
C40 | 0.62661 (11) | 0.16657 (14) | 0.30854 (10) | 0.0130 (4) | |
C41 | 0.67797 (12) | 0.15686 (14) | 0.37396 (11) | 0.0168 (4) | |
H41 | 0.7295 | 0.1746 | 0.3815 | 0.020* | |
C42 | 0.65307 (12) | 0.12073 (15) | 0.42832 (11) | 0.0185 (4) | |
H42 | 0.6872 | 0.1140 | 0.4738 | 0.022* | |
C43 | 0.57783 (12) | 0.09455 (15) | 0.41542 (11) | 0.0179 (4) | |
H43 | 0.5598 | 0.0688 | 0.4518 | 0.021* | |
C44 | 0.52923 (12) | 0.10627 (15) | 0.34899 (10) | 0.0163 (4) | |
H44 | 0.4778 | 0.0875 | 0.3401 | 0.020* | |
Cl2 | 0.13663 (3) | 0.53482 (3) | 0.09108 (2) | 0.01590 (10) | |
O5 | 0.17327 (11) | 0.54635 (16) | 0.16497 (9) | 0.0475 (6) | |
O6 | 0.10631 (10) | 0.62578 (12) | 0.06535 (9) | 0.0315 (4) | |
O7 | 0.19014 (9) | 0.50453 (14) | 0.05582 (9) | 0.0357 (5) | |
O8 | 0.07645 (11) | 0.46716 (13) | 0.08013 (11) | 0.0414 (5) | |
Cl4 | 0.35586 (3) | 0.04176 (3) | 0.41789 (2) | 0.01382 (10) | |
O13 | 0.32469 (9) | 0.08657 (11) | 0.35075 (8) | 0.0247 (4) | |
O14 | 0.42674 (9) | 0.08605 (12) | 0.45328 (9) | 0.0279 (4) | |
O15 | 0.36737 (10) | −0.05777 (11) | 0.40840 (9) | 0.0320 (4) | |
O16 | 0.30413 (8) | 0.05344 (12) | 0.45972 (8) | 0.0232 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01092 (12) | 0.00992 (12) | 0.00883 (11) | −0.00099 (9) | 0.00425 (9) | −0.00156 (9) |
Cl1 | 0.0153 (2) | 0.0108 (2) | 0.0154 (2) | 0.00036 (18) | 0.00400 (18) | −0.00081 (18) |
O1 | 0.0192 (8) | 0.0103 (7) | 0.0243 (8) | 0.0011 (6) | 0.0070 (6) | −0.0006 (6) |
O2 | 0.0443 (11) | 0.0272 (9) | 0.0278 (9) | −0.0037 (8) | 0.0222 (8) | 0.0020 (7) |
O3 | 0.0180 (8) | 0.0125 (7) | 0.0416 (10) | 0.0043 (6) | 0.0025 (7) | −0.0011 (7) |
O4 | 0.0267 (9) | 0.0212 (8) | 0.0226 (8) | −0.0024 (7) | −0.0027 (7) | −0.0052 (7) |
N1 | 0.0143 (8) | 0.0110 (8) | 0.0123 (8) | −0.0019 (6) | 0.0058 (7) | −0.0007 (6) |
N2 | 0.0122 (8) | 0.0102 (8) | 0.0099 (8) | 0.0012 (6) | 0.0046 (6) | 0.0003 (6) |
N3 | 0.0117 (8) | 0.0098 (8) | 0.0092 (8) | 0.0024 (6) | 0.0029 (6) | 0.0012 (6) |
N4 | 0.0115 (8) | 0.0105 (8) | 0.0101 (8) | −0.0004 (6) | 0.0022 (6) | 0.0003 (6) |
C1 | 0.0160 (10) | 0.0125 (10) | 0.0165 (10) | −0.0027 (8) | 0.0082 (8) | −0.0006 (8) |
C2 | 0.0210 (11) | 0.0147 (10) | 0.0132 (10) | −0.0051 (8) | 0.0076 (8) | −0.0022 (8) |
C3 | 0.0205 (11) | 0.0164 (10) | 0.0115 (10) | −0.0055 (8) | 0.0038 (8) | 0.0029 (8) |
C4 | 0.0162 (10) | 0.0133 (10) | 0.0127 (9) | −0.0001 (8) | 0.0036 (8) | 0.0030 (8) |
C5 | 0.0151 (9) | 0.0107 (9) | 0.0134 (9) | −0.0003 (8) | 0.0055 (8) | 0.0024 (7) |
C6 | 0.0146 (9) | 0.0133 (10) | 0.0115 (9) | 0.0036 (8) | 0.0040 (8) | 0.0026 (8) |
C7 | 0.0140 (9) | 0.0115 (9) | 0.0125 (9) | −0.0016 (7) | 0.0040 (8) | 0.0007 (7) |
C8 | 0.0137 (10) | 0.0204 (11) | 0.0164 (10) | −0.0042 (8) | 0.0046 (8) | 0.0025 (8) |
C9 | 0.0142 (10) | 0.0261 (12) | 0.0180 (11) | −0.0015 (9) | 0.0091 (8) | 0.0019 (9) |
C10 | 0.0155 (10) | 0.0217 (11) | 0.0161 (10) | 0.0042 (8) | 0.0085 (8) | −0.0015 (8) |
C11 | 0.0129 (9) | 0.0118 (9) | 0.0105 (9) | 0.0024 (7) | 0.0037 (7) | −0.0001 (7) |
C12 | 0.0129 (9) | 0.0132 (10) | 0.0105 (9) | 0.0002 (7) | 0.0063 (7) | −0.0016 (7) |
C13 | 0.0168 (10) | 0.0194 (10) | 0.0103 (9) | −0.0012 (8) | 0.0039 (8) | 0.0041 (8) |
C14 | 0.0200 (11) | 0.0196 (11) | 0.0118 (10) | −0.0004 (9) | 0.0026 (8) | 0.0054 (8) |
C15 | 0.0189 (11) | 0.0187 (11) | 0.0163 (10) | 0.0035 (8) | 0.0033 (8) | 0.0018 (8) |
C16 | 0.0117 (9) | 0.0222 (11) | 0.0137 (10) | 0.0041 (8) | 0.0030 (8) | 0.0021 (8) |
C17 | 0.0151 (9) | 0.0092 (9) | 0.0109 (9) | −0.0017 (7) | 0.0055 (7) | −0.0018 (7) |
C18 | 0.0121 (9) | 0.0107 (9) | 0.0113 (9) | 0.0016 (7) | 0.0024 (7) | 0.0027 (7) |
C19 | 0.0147 (10) | 0.0101 (9) | 0.0156 (10) | −0.0008 (8) | 0.0029 (8) | −0.0010 (8) |
C20 | 0.0114 (9) | 0.0131 (10) | 0.0168 (10) | −0.0012 (7) | 0.0017 (8) | 0.0036 (8) |
C21 | 0.0118 (9) | 0.0173 (10) | 0.0121 (9) | 0.0015 (8) | 0.0040 (7) | 0.0031 (8) |
C22 | 0.0152 (10) | 0.0141 (10) | 0.0110 (9) | 0.0018 (8) | 0.0045 (8) | 0.0007 (7) |
Cu2 | 0.01328 (12) | 0.01163 (12) | 0.00875 (11) | 0.00174 (9) | 0.00442 (9) | 0.00256 (9) |
Cl3 | 0.0146 (2) | 0.0129 (2) | 0.0184 (2) | −0.00165 (18) | 0.00546 (19) | 0.00010 (18) |
O9 | 0.0307 (9) | 0.0131 (7) | 0.0255 (8) | −0.0051 (6) | 0.0117 (7) | −0.0009 (6) |
O10 | 0.0549 (12) | 0.0363 (11) | 0.0472 (12) | −0.0129 (9) | 0.0382 (10) | −0.0172 (9) |
O11 | 0.0146 (8) | 0.0214 (8) | 0.0426 (10) | −0.0051 (6) | 0.0019 (7) | 0.0022 (7) |
O12 | 0.0332 (10) | 0.0255 (9) | 0.0371 (10) | 0.0049 (8) | −0.0098 (8) | 0.0081 (8) |
N5 | 0.0120 (8) | 0.0108 (8) | 0.0105 (8) | −0.0012 (6) | 0.0010 (6) | −0.0008 (6) |
N6 | 0.0169 (8) | 0.0118 (8) | 0.0095 (8) | −0.0039 (7) | 0.0043 (7) | −0.0005 (6) |
N7 | 0.0148 (8) | 0.0085 (8) | 0.0107 (8) | −0.0003 (6) | 0.0061 (6) | 0.0005 (6) |
N8 | 0.0144 (8) | 0.0159 (9) | 0.0124 (8) | 0.0028 (7) | 0.0048 (7) | 0.0017 (7) |
C23 | 0.0166 (10) | 0.0152 (10) | 0.0118 (9) | −0.0019 (8) | 0.0037 (8) | −0.0005 (8) |
C24 | 0.0144 (10) | 0.0180 (10) | 0.0177 (10) | −0.0038 (8) | 0.0037 (8) | −0.0042 (8) |
C25 | 0.0119 (10) | 0.0175 (10) | 0.0226 (11) | 0.0009 (8) | 0.0003 (8) | −0.0045 (9) |
C26 | 0.0161 (10) | 0.0149 (10) | 0.0159 (10) | −0.0001 (8) | 0.0002 (8) | −0.0004 (8) |
C27 | 0.0131 (9) | 0.0112 (9) | 0.0131 (9) | −0.0027 (7) | 0.0006 (7) | −0.0016 (7) |
C28 | 0.0187 (10) | 0.0109 (9) | 0.0120 (9) | 0.0008 (8) | 0.0035 (8) | 0.0019 (7) |
C29 | 0.0229 (11) | 0.0168 (11) | 0.0150 (10) | −0.0077 (8) | 0.0032 (9) | −0.0015 (8) |
C30 | 0.0250 (12) | 0.0214 (11) | 0.0146 (10) | −0.0032 (9) | 0.0008 (9) | −0.0020 (9) |
C31 | 0.0315 (13) | 0.0264 (12) | 0.0108 (10) | 0.0033 (10) | 0.0013 (9) | −0.0030 (9) |
C32 | 0.0251 (11) | 0.0198 (11) | 0.0130 (10) | 0.0022 (9) | 0.0048 (9) | −0.0029 (8) |
C33 | 0.0215 (10) | 0.0122 (10) | 0.0114 (9) | −0.0005 (8) | 0.0070 (8) | 0.0018 (8) |
C34 | 0.0212 (10) | 0.0103 (9) | 0.0112 (9) | −0.0023 (8) | 0.0089 (8) | 0.0014 (7) |
C35 | 0.0226 (11) | 0.0158 (10) | 0.0193 (11) | −0.0053 (8) | 0.0128 (9) | −0.0004 (8) |
C36 | 0.0187 (10) | 0.0194 (11) | 0.0208 (11) | −0.0015 (8) | 0.0133 (9) | −0.0024 (9) |
C37 | 0.0154 (10) | 0.0145 (10) | 0.0220 (11) | 0.0000 (8) | 0.0091 (8) | −0.0020 (8) |
C38 | 0.0149 (10) | 0.0093 (9) | 0.0143 (10) | −0.0012 (7) | 0.0056 (8) | 0.0001 (7) |
C39 | 0.0160 (10) | 0.0129 (10) | 0.0146 (10) | −0.0024 (8) | 0.0054 (8) | −0.0013 (8) |
C40 | 0.0166 (10) | 0.0090 (9) | 0.0139 (10) | 0.0005 (7) | 0.0049 (8) | −0.0011 (7) |
C41 | 0.0188 (10) | 0.0149 (10) | 0.0161 (10) | −0.0005 (8) | 0.0037 (8) | −0.0008 (8) |
C42 | 0.0247 (11) | 0.0177 (10) | 0.0119 (10) | 0.0058 (9) | 0.0032 (8) | 0.0013 (8) |
C43 | 0.0223 (11) | 0.0209 (11) | 0.0128 (10) | 0.0067 (9) | 0.0085 (8) | 0.0058 (8) |
C44 | 0.0178 (10) | 0.0173 (10) | 0.0155 (10) | 0.0051 (8) | 0.0074 (8) | 0.0049 (8) |
Cl2 | 0.0177 (2) | 0.0153 (2) | 0.0144 (2) | 0.00492 (19) | 0.00411 (19) | 0.00103 (18) |
O5 | 0.0500 (12) | 0.0691 (15) | 0.0169 (9) | 0.0306 (11) | −0.0009 (8) | −0.0063 (9) |
O6 | 0.0397 (10) | 0.0210 (9) | 0.0356 (10) | 0.0080 (7) | 0.0135 (8) | 0.0125 (7) |
O7 | 0.0188 (8) | 0.0560 (12) | 0.0328 (10) | 0.0023 (8) | 0.0081 (7) | −0.0250 (9) |
O8 | 0.0522 (12) | 0.0215 (9) | 0.0630 (13) | −0.0147 (8) | 0.0366 (11) | −0.0078 (9) |
Cl4 | 0.0155 (2) | 0.0131 (2) | 0.0130 (2) | −0.00116 (18) | 0.00433 (18) | −0.00055 (18) |
O13 | 0.0328 (9) | 0.0248 (9) | 0.0173 (8) | 0.0013 (7) | 0.0086 (7) | 0.0078 (7) |
O14 | 0.0175 (8) | 0.0371 (10) | 0.0300 (9) | −0.0103 (7) | 0.0085 (7) | −0.0118 (8) |
O15 | 0.0502 (11) | 0.0169 (8) | 0.0250 (9) | 0.0078 (8) | 0.0043 (8) | −0.0031 (7) |
O16 | 0.0184 (8) | 0.0351 (9) | 0.0187 (8) | 0.0021 (7) | 0.0095 (6) | 0.0066 (7) |
Cu1—O1 | 2.2038 (14) | Cu2—N8 | 1.9890 (16) |
Cu1—N1 | 1.9808 (16) | Cl3—O9 | 1.4530 (15) |
Cu1—N2 | 2.0349 (16) | Cl3—O10 | 1.4302 (18) |
Cu1—N3 | 2.0365 (16) | Cl3—O11 | 1.4316 (15) |
Cu1—N4 | 2.0309 (16) | Cl3—O12 | 1.4311 (17) |
Cl1—O1 | 1.4695 (14) | N5—C23 | 1.343 (2) |
Cl1—O2 | 1.4311 (16) | N5—C27 | 1.347 (3) |
Cl1—O3 | 1.4306 (15) | N6—C28 | 1.491 (3) |
Cl1—O4 | 1.4301 (15) | N6—C29 | 1.506 (3) |
N1—C1 | 1.343 (2) | N6—C33 | 1.517 (2) |
N1—C5 | 1.351 (3) | N7—C34 | 1.505 (2) |
N2—C6 | 1.492 (2) | N7—C38 | 1.499 (2) |
N2—C7 | 1.503 (2) | N7—C39 | 1.488 (2) |
N2—C11 | 1.505 (2) | N8—C40 | 1.352 (3) |
N3—C12 | 1.516 (2) | N8—C44 | 1.344 (3) |
N3—C16 | 1.509 (2) | C23—H23 | 0.9500 |
N3—C17 | 1.500 (2) | C23—C24 | 1.383 (3) |
N4—C18 | 1.349 (2) | C24—H24 | 0.9500 |
N4—C22 | 1.343 (2) | C24—C25 | 1.383 (3) |
C1—H1 | 0.9500 | C25—H25 | 0.9500 |
C1—C2 | 1.382 (3) | C25—C26 | 1.389 (3) |
C2—H2 | 0.9500 | C26—H26 | 0.9500 |
C2—C3 | 1.391 (3) | C26—C27 | 1.384 (3) |
C3—H3 | 0.9500 | C27—C28 | 1.505 (3) |
C3—C4 | 1.386 (3) | C28—H28A | 0.9900 |
C4—H4 | 0.9500 | C28—H28B | 0.9900 |
C4—C5 | 1.381 (3) | C29—H29A | 0.9900 |
C5—C6 | 1.506 (3) | C29—H29B | 0.9900 |
C6—H6A | 0.9900 | C29—C30 | 1.518 (3) |
C6—H6B | 0.9900 | C30—H30A | 0.9900 |
C7—H7A | 0.9900 | C30—H30B | 0.9900 |
C7—H7B | 0.9900 | C30—C31 | 1.536 (3) |
C7—C8 | 1.525 (3) | C31—H31A | 0.9900 |
C8—H8A | 0.9900 | C31—H31B | 0.9900 |
C8—H8B | 0.9900 | C31—C32 | 1.535 (3) |
C8—C9 | 1.524 (3) | C32—H32A | 0.9900 |
C9—H9A | 0.9900 | C32—H32B | 0.9900 |
C9—H9B | 0.9900 | C32—C33 | 1.526 (3) |
C9—C10 | 1.534 (3) | C33—H33 | 1.0000 |
C10—H10A | 0.9900 | C33—C34 | 1.547 (3) |
C10—H10B | 0.9900 | C34—H34 | 1.0000 |
C10—C11 | 1.542 (3) | C34—C35 | 1.539 (3) |
C11—H11 | 1.0000 | C35—H35A | 0.9900 |
C11—C12 | 1.546 (3) | C35—H35B | 0.9900 |
C12—H12 | 1.0000 | C35—C36 | 1.535 (3) |
C12—C13 | 1.525 (3) | C36—H36A | 0.9900 |
C13—H13A | 0.9900 | C36—H36B | 0.9900 |
C13—H13B | 0.9900 | C36—C37 | 1.520 (3) |
C13—C14 | 1.516 (3) | C37—H37A | 0.9900 |
C14—H14A | 0.9900 | C37—H37B | 0.9900 |
C14—H14B | 0.9900 | C37—C38 | 1.523 (3) |
C14—C15 | 1.526 (3) | C38—H38A | 0.9900 |
C15—H15A | 0.9900 | C38—H38B | 0.9900 |
C15—H15B | 0.9900 | C39—H39A | 0.9900 |
C15—C16 | 1.508 (3) | C39—H39B | 0.9900 |
C16—H16A | 0.9900 | C39—C40 | 1.501 (3) |
C16—H16B | 0.9900 | C40—C41 | 1.383 (3) |
C17—H17A | 0.9900 | C41—H41 | 0.9500 |
C17—H17B | 0.9900 | C41—C42 | 1.387 (3) |
C17—C18 | 1.508 (3) | C42—H42 | 0.9500 |
C18—C19 | 1.383 (3) | C42—C43 | 1.384 (3) |
C19—H19 | 0.9500 | C43—H43 | 0.9500 |
C19—C20 | 1.389 (3) | C43—C44 | 1.381 (3) |
C20—H20 | 0.9500 | C44—H44 | 0.9500 |
C20—C21 | 1.384 (3) | Cl2—O5 | 1.4442 (18) |
C21—H21 | 0.9500 | Cl2—O6 | 1.4260 (16) |
C21—C22 | 1.386 (3) | Cl2—O7 | 1.4278 (16) |
C22—H22 | 0.9500 | Cl2—O8 | 1.4264 (18) |
Cu2—O9 | 2.3438 (15) | Cl4—O13 | 1.4415 (15) |
Cu2—N5 | 1.9901 (16) | Cl4—O14 | 1.4355 (16) |
Cu2—N6 | 2.0226 (16) | Cl4—O15 | 1.4302 (16) |
Cu2—N7 | 2.0078 (16) | Cl4—O16 | 1.4426 (15) |
N1—Cu1—O1 | 96.20 (6) | N8—Cu2—O9 | 89.24 (6) |
N1—Cu1—N2 | 82.45 (6) | N8—Cu2—N5 | 103.00 (7) |
N1—Cu1—N3 | 164.41 (7) | N8—Cu2—N6 | 168.41 (7) |
N1—Cu1—N4 | 98.15 (6) | N8—Cu2—N7 | 82.92 (7) |
N2—Cu1—O1 | 126.30 (6) | O10—Cl3—O9 | 108.58 (10) |
N2—Cu1—N3 | 87.19 (6) | O10—Cl3—O11 | 110.02 (11) |
N3—Cu1—O1 | 99.32 (6) | O10—Cl3—O12 | 110.39 (12) |
N4—Cu1—O1 | 91.27 (6) | O11—Cl3—O9 | 109.11 (10) |
N4—Cu1—N2 | 142.29 (6) | O12—Cl3—O9 | 109.25 (10) |
N4—Cu1—N3 | 83.01 (6) | O12—Cl3—O11 | 109.46 (11) |
O2—Cl1—O1 | 108.63 (9) | Cl3—O9—Cu2 | 138.24 (10) |
O3—Cl1—O1 | 107.93 (9) | C23—N5—Cu2 | 129.19 (14) |
O3—Cl1—O2 | 110.69 (11) | C23—N5—C27 | 119.21 (17) |
O4—Cl1—O1 | 108.97 (9) | C27—N5—Cu2 | 111.60 (13) |
O4—Cl1—O2 | 110.01 (10) | C28—N6—Cu2 | 102.07 (11) |
O4—Cl1—O3 | 110.56 (10) | C28—N6—C29 | 110.32 (16) |
Cl1—O1—Cu1 | 130.44 (9) | C28—N6—C33 | 110.81 (15) |
C1—N1—Cu1 | 129.13 (14) | C29—N6—Cu2 | 110.23 (12) |
C1—N1—C5 | 119.14 (17) | C29—N6—C33 | 112.00 (15) |
C5—N1—Cu1 | 111.68 (13) | C33—N6—Cu2 | 110.99 (12) |
C6—N2—Cu1 | 101.34 (11) | C34—N7—Cu2 | 106.98 (12) |
C6—N2—C7 | 108.77 (15) | C38—N7—Cu2 | 111.13 (12) |
C6—N2—C11 | 110.92 (14) | C38—N7—C34 | 113.38 (15) |
C7—N2—Cu1 | 113.53 (11) | C39—N7—Cu2 | 103.32 (11) |
C7—N2—C11 | 114.52 (15) | C39—N7—C34 | 111.19 (15) |
C11—N2—Cu1 | 106.99 (11) | C39—N7—C38 | 110.33 (15) |
C12—N3—Cu1 | 108.57 (11) | C40—N8—Cu2 | 111.12 (13) |
C16—N3—Cu1 | 118.99 (12) | C44—N8—Cu2 | 129.77 (14) |
C16—N3—C12 | 113.91 (14) | C44—N8—C40 | 119.06 (17) |
C17—N3—Cu1 | 98.75 (11) | N5—C23—H23 | 119.1 |
C17—N3—C12 | 110.92 (14) | N5—C23—C24 | 121.90 (19) |
C17—N3—C16 | 104.40 (15) | C24—C23—H23 | 119.1 |
C18—N4—Cu1 | 110.03 (12) | C23—C24—H24 | 120.5 |
C22—N4—Cu1 | 130.98 (13) | C25—C24—C23 | 119.0 (2) |
C22—N4—C18 | 118.95 (17) | C25—C24—H24 | 120.5 |
N1—C1—H1 | 119.1 | C24—C25—H25 | 120.4 |
N1—C1—C2 | 121.75 (19) | C24—C25—C26 | 119.14 (19) |
C2—C1—H1 | 119.1 | C26—C25—H25 | 120.4 |
C1—C2—H2 | 120.5 | C25—C26—H26 | 120.6 |
C1—C2—C3 | 119.08 (19) | C27—C26—C25 | 118.89 (19) |
C3—C2—H2 | 120.5 | C27—C26—H26 | 120.6 |
C2—C3—H3 | 120.4 | N5—C27—C26 | 121.78 (19) |
C4—C3—C2 | 119.17 (19) | N5—C27—C28 | 114.74 (17) |
C4—C3—H3 | 120.4 | C26—C27—C28 | 123.47 (18) |
C3—C4—H4 | 120.6 | N6—C28—C27 | 109.16 (16) |
C5—C4—C3 | 118.75 (19) | N6—C28—H28A | 109.8 |
C5—C4—H4 | 120.6 | N6—C28—H28B | 109.8 |
N1—C5—C4 | 122.09 (18) | C27—C28—H28A | 109.8 |
N1—C5—C6 | 114.54 (17) | C27—C28—H28B | 109.8 |
C4—C5—C6 | 123.37 (18) | H28A—C28—H28B | 108.3 |
N2—C6—C5 | 108.85 (15) | N6—C29—H29A | 109.0 |
N2—C6—H6A | 109.9 | N6—C29—H29B | 109.0 |
N2—C6—H6B | 109.9 | N6—C29—C30 | 112.80 (17) |
C5—C6—H6A | 109.9 | H29A—C29—H29B | 107.8 |
C5—C6—H6B | 109.9 | C30—C29—H29A | 109.0 |
H6A—C6—H6B | 108.3 | C30—C29—H29B | 109.0 |
N2—C7—H7A | 109.0 | C29—C30—H30A | 109.5 |
N2—C7—H7B | 109.0 | C29—C30—H30B | 109.5 |
N2—C7—C8 | 113.12 (16) | C29—C30—C31 | 110.53 (18) |
H7A—C7—H7B | 107.8 | H30A—C30—H30B | 108.1 |
C8—C7—H7A | 109.0 | C31—C30—H30A | 109.5 |
C8—C7—H7B | 109.0 | C31—C30—H30B | 109.5 |
C7—C8—H8A | 109.7 | C30—C31—H31A | 109.2 |
C7—C8—H8B | 109.7 | C30—C31—H31B | 109.2 |
H8A—C8—H8B | 108.2 | H31A—C31—H31B | 107.9 |
C9—C8—C7 | 109.79 (16) | C32—C31—C30 | 111.86 (18) |
C9—C8—H8A | 109.7 | C32—C31—H31A | 109.2 |
C9—C8—H8B | 109.7 | C32—C31—H31B | 109.2 |
C8—C9—H9A | 109.6 | C31—C32—H32A | 109.8 |
C8—C9—H9B | 109.6 | C31—C32—H32B | 109.8 |
C8—C9—C10 | 110.16 (17) | H32A—C32—H32B | 108.2 |
H9A—C9—H9B | 108.1 | C33—C32—C31 | 109.47 (18) |
C10—C9—H9A | 109.6 | C33—C32—H32A | 109.8 |
C10—C9—H9B | 109.6 | C33—C32—H32B | 109.8 |
C9—C10—H10A | 108.4 | N6—C33—C32 | 110.92 (16) |
C9—C10—H10B | 108.4 | N6—C33—H33 | 106.0 |
C9—C10—C11 | 115.50 (16) | N6—C33—C34 | 108.61 (15) |
H10A—C10—H10B | 107.5 | C32—C33—H33 | 106.0 |
C11—C10—H10A | 108.4 | C32—C33—C34 | 118.57 (17) |
C11—C10—H10B | 108.4 | C34—C33—H33 | 106.0 |
N2—C11—C10 | 113.86 (16) | N7—C34—C33 | 112.09 (15) |
N2—C11—H11 | 105.5 | N7—C34—H34 | 105.5 |
N2—C11—C12 | 111.11 (15) | N7—C34—C35 | 112.40 (16) |
C10—C11—H11 | 105.5 | C33—C34—H34 | 105.5 |
C10—C11—C12 | 114.29 (16) | C35—C34—C33 | 115.00 (16) |
C12—C11—H11 | 105.5 | C35—C34—H34 | 105.5 |
N3—C12—C11 | 108.21 (15) | C34—C35—H35A | 108.6 |
N3—C12—H12 | 107.1 | C34—C35—H35B | 108.6 |
N3—C12—C13 | 112.09 (15) | H35A—C35—H35B | 107.6 |
C11—C12—H12 | 107.1 | C36—C35—C34 | 114.67 (16) |
C13—C12—C11 | 114.99 (16) | C36—C35—H35A | 108.6 |
C13—C12—H12 | 107.1 | C36—C35—H35B | 108.6 |
C12—C13—H13A | 109.0 | C35—C36—H36A | 109.5 |
C12—C13—H13B | 109.0 | C35—C36—H36B | 109.5 |
H13A—C13—H13B | 107.8 | H36A—C36—H36B | 108.0 |
C14—C13—C12 | 112.76 (17) | C37—C36—C35 | 110.90 (17) |
C14—C13—H13A | 109.0 | C37—C36—H36A | 109.5 |
C14—C13—H13B | 109.0 | C37—C36—H36B | 109.5 |
C13—C14—H14A | 110.1 | C36—C37—H37A | 109.6 |
C13—C14—H14B | 110.1 | C36—C37—H37B | 109.6 |
C13—C14—C15 | 108.06 (17) | C36—C37—C38 | 110.21 (17) |
H14A—C14—H14B | 108.4 | H37A—C37—H37B | 108.1 |
C15—C14—H14A | 110.1 | C38—C37—H37A | 109.6 |
C15—C14—H14B | 110.1 | C38—C37—H37B | 109.6 |
C14—C15—H15A | 109.9 | N7—C38—C37 | 112.68 (16) |
C14—C15—H15B | 109.9 | N7—C38—H38A | 109.1 |
H15A—C15—H15B | 108.3 | N7—C38—H38B | 109.1 |
C16—C15—C14 | 108.97 (17) | C37—C38—H38A | 109.1 |
C16—C15—H15A | 109.9 | C37—C38—H38B | 109.1 |
C16—C15—H15B | 109.9 | H38A—C38—H38B | 107.8 |
N3—C16—H16A | 108.3 | N7—C39—H39A | 109.8 |
N3—C16—H16B | 108.3 | N7—C39—H39B | 109.8 |
C15—C16—N3 | 116.14 (17) | N7—C39—C40 | 109.50 (16) |
C15—C16—H16A | 108.3 | H39A—C39—H39B | 108.2 |
C15—C16—H16B | 108.3 | C40—C39—H39A | 109.8 |
H16A—C16—H16B | 107.4 | C40—C39—H39B | 109.8 |
N3—C17—H17A | 110.0 | N8—C40—C39 | 115.35 (17) |
N3—C17—H17B | 110.0 | N8—C40—C41 | 121.76 (18) |
N3—C17—C18 | 108.44 (15) | C41—C40—C39 | 122.89 (18) |
H17A—C17—H17B | 108.4 | C40—C41—H41 | 120.5 |
C18—C17—H17A | 110.0 | C40—C41—C42 | 118.9 (2) |
C18—C17—H17B | 110.0 | C42—C41—H41 | 120.5 |
N4—C18—C17 | 113.71 (16) | C41—C42—H42 | 120.4 |
N4—C18—C19 | 122.12 (18) | C43—C42—C41 | 119.14 (19) |
C19—C18—C17 | 124.17 (17) | C43—C42—H42 | 120.4 |
C18—C19—H19 | 120.6 | C42—C43—H43 | 120.4 |
C18—C19—C20 | 118.81 (18) | C44—C43—C42 | 119.19 (19) |
C20—C19—H19 | 120.6 | C44—C43—H43 | 120.4 |
C19—C20—H20 | 120.5 | N8—C44—C43 | 121.84 (19) |
C21—C20—C19 | 119.02 (18) | N8—C44—H44 | 119.1 |
C21—C20—H20 | 120.5 | C43—C44—H44 | 119.1 |
C20—C21—H21 | 120.4 | O6—Cl2—O5 | 106.77 (11) |
C20—C21—C22 | 119.21 (18) | O6—Cl2—O7 | 110.02 (11) |
C22—C21—H21 | 120.4 | O6—Cl2—O8 | 109.30 (11) |
N4—C22—C21 | 121.80 (18) | O7—Cl2—O5 | 110.38 (11) |
N4—C22—H22 | 119.1 | O8—Cl2—O5 | 110.33 (13) |
C21—C22—H22 | 119.1 | O8—Cl2—O7 | 109.99 (11) |
N5—Cu2—O9 | 85.54 (6) | O13—Cl4—O16 | 109.50 (9) |
N5—Cu2—N6 | 83.25 (7) | O14—Cl4—O13 | 109.54 (10) |
N5—Cu2—N7 | 151.39 (7) | O14—Cl4—O16 | 108.91 (9) |
N6—Cu2—O9 | 101.07 (6) | O15—Cl4—O13 | 109.63 (10) |
N7—Cu2—O9 | 122.81 (6) | O15—Cl4—O14 | 109.74 (11) |
N7—Cu2—N6 | 87.02 (7) | O15—Cl4—O16 | 109.50 (10) |
Cu1—N1—C1—C2 | −175.28 (14) | Cu2—N5—C23—C24 | 178.98 (14) |
Cu1—N1—C5—C4 | 176.50 (15) | Cu2—N5—C27—C26 | 179.37 (15) |
Cu1—N1—C5—C6 | −3.5 (2) | Cu2—N5—C27—C28 | −0.6 (2) |
Cu1—N2—C6—C5 | 46.04 (16) | Cu2—N6—C28—C27 | −44.90 (16) |
Cu1—N2—C7—C8 | 173.81 (12) | Cu2—N6—C29—C30 | −170.51 (14) |
Cu1—N2—C11—C10 | −167.28 (13) | Cu2—N6—C33—C32 | 110.08 (15) |
Cu1—N2—C11—C12 | −36.51 (17) | Cu2—N6—C33—C34 | −21.90 (18) |
Cu1—N3—C12—C11 | −34.01 (17) | Cu2—N7—C34—C33 | −38.73 (17) |
Cu1—N3—C12—C13 | 93.82 (15) | Cu2—N7—C34—C35 | −170.07 (13) |
Cu1—N3—C16—C15 | −86.24 (19) | Cu2—N7—C38—C37 | 174.97 (13) |
Cu1—N3—C17—C18 | −52.50 (15) | Cu2—N7—C39—C40 | 41.98 (17) |
Cu1—N4—C18—C17 | −4.93 (19) | Cu2—N8—C40—C39 | −5.7 (2) |
Cu1—N4—C18—C19 | 175.14 (15) | Cu2—N8—C40—C41 | 174.63 (15) |
Cu1—N4—C22—C21 | −177.14 (14) | Cu2—N8—C44—C43 | −174.34 (15) |
O2—Cl1—O1—Cu1 | −54.85 (14) | O10—Cl3—O9—Cu2 | −36.13 (18) |
O3—Cl1—O1—Cu1 | −174.91 (11) | O11—Cl3—O9—Cu2 | −156.04 (13) |
O4—Cl1—O1—Cu1 | 64.99 (14) | O12—Cl3—O9—Cu2 | 84.32 (16) |
N1—C1—C2—C3 | −1.4 (3) | N5—C23—C24—C25 | 1.6 (3) |
N1—C5—C6—N2 | −30.3 (2) | N5—C27—C28—N6 | 32.0 (2) |
N2—C7—C8—C9 | −59.0 (2) | N6—C29—C30—C31 | 58.1 (2) |
N2—C11—C12—N3 | 47.6 (2) | N6—C33—C34—N7 | 40.4 (2) |
N2—C11—C12—C13 | −78.6 (2) | N6—C33—C34—C35 | 170.37 (16) |
N3—C12—C13—C14 | 52.1 (2) | N7—C34—C35—C36 | 45.8 (2) |
N3—C17—C18—N4 | 40.7 (2) | N7—C39—C40—N8 | −25.4 (2) |
N3—C17—C18—C19 | −139.32 (19) | N7—C39—C40—C41 | 154.29 (18) |
N4—C18—C19—C20 | 2.5 (3) | N8—C40—C41—C42 | 1.3 (3) |
C1—N1—C5—C4 | −1.0 (3) | C23—N5—C27—C26 | −0.9 (3) |
C1—N1—C5—C6 | 179.06 (17) | C23—N5—C27—C28 | 179.11 (17) |
C1—C2—C3—C4 | 0.3 (3) | C23—C24—C25—C26 | −0.9 (3) |
C2—C3—C4—C5 | 0.3 (3) | C24—C25—C26—C27 | −0.6 (3) |
C3—C4—C5—N1 | 0.0 (3) | C25—C26—C27—N5 | 1.5 (3) |
C3—C4—C5—C6 | 179.92 (18) | C25—C26—C27—C28 | −178.48 (18) |
C4—C5—C6—N2 | 149.75 (18) | C26—C27—C28—N6 | −147.94 (18) |
C5—N1—C1—C2 | 1.7 (3) | C27—N5—C23—C24 | −0.7 (3) |
C6—N2—C7—C8 | −74.19 (19) | C28—N6—C29—C30 | 77.5 (2) |
C6—N2—C11—C10 | 83.02 (19) | C28—N6—C33—C32 | −137.26 (17) |
C6—N2—C11—C12 | −146.20 (16) | C28—N6—C33—C34 | 90.76 (18) |
C7—N2—C6—C5 | −73.84 (19) | C29—N6—C28—C27 | 72.24 (19) |
C7—N2—C11—C10 | −40.5 (2) | C29—N6—C33—C32 | −13.6 (2) |
C7—N2—C11—C12 | 90.23 (19) | C29—N6—C33—C34 | −145.58 (16) |
C7—C8—C9—C10 | 57.4 (2) | C29—C30—C31—C32 | −8.0 (3) |
C8—C9—C10—C11 | −49.8 (2) | C30—C31—C32—C33 | −50.1 (2) |
C9—C10—C11—N2 | 41.2 (2) | C31—C32—C33—N6 | 62.5 (2) |
C9—C10—C11—C12 | −88.0 (2) | C31—C32—C33—C34 | −170.86 (17) |
C10—C11—C12—N3 | 178.10 (15) | C32—C33—C34—N7 | −87.4 (2) |
C10—C11—C12—C13 | 51.9 (2) | C32—C33—C34—C35 | 42.6 (2) |
C11—N2—C6—C5 | 159.35 (15) | C33—N6—C28—C27 | −163.14 (15) |
C11—N2—C7—C8 | 50.5 (2) | C33—N6—C29—C30 | −46.4 (2) |
C11—C12—C13—C14 | 176.20 (16) | C33—C34—C35—C36 | −84.0 (2) |
C12—N3—C16—C15 | 43.8 (2) | C34—N7—C38—C37 | 54.4 (2) |
C12—N3—C17—C18 | −166.32 (15) | C34—N7—C39—C40 | 156.41 (16) |
C12—C13—C14—C15 | −62.0 (2) | C34—C35—C36—C37 | −50.2 (2) |
C13—C14—C15—C16 | 60.5 (2) | C35—C36—C37—C38 | 54.9 (2) |
C14—C15—C16—N3 | −53.3 (2) | C36—C37—C38—N7 | −58.0 (2) |
C16—N3—C12—C11 | −169.10 (15) | C38—N7—C34—C33 | 84.1 (2) |
C16—N3—C12—C13 | −41.3 (2) | C38—N7—C34—C35 | −47.2 (2) |
C16—N3—C17—C18 | 70.58 (18) | C38—N7—C39—C40 | −76.89 (19) |
C17—N3—C12—C11 | 73.46 (18) | C39—N7—C34—C33 | −150.87 (16) |
C17—N3—C12—C13 | −158.70 (16) | C39—N7—C34—C35 | 77.8 (2) |
C17—N3—C16—C15 | 164.99 (17) | C39—N7—C38—C37 | −71.0 (2) |
C17—C18—C19—C20 | −177.39 (18) | C39—C40—C41—C42 | −178.41 (19) |
C18—N4—C22—C21 | 0.3 (3) | C40—N8—C44—C43 | 2.7 (3) |
C18—C19—C20—C21 | 0.2 (3) | C40—C41—C42—C43 | 0.7 (3) |
C19—C20—C21—C22 | −2.6 (3) | C41—C42—C43—C44 | −0.9 (3) |
C20—C21—C22—N4 | 2.4 (3) | C42—C43—C44—N8 | −0.8 (3) |
C22—N4—C18—C17 | 177.15 (16) | C44—N8—C40—C39 | 176.75 (17) |
C22—N4—C18—C19 | −2.8 (3) | C44—N8—C40—C41 | −2.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O8 | 0.95 | 2.62 | 3.259 (3) | 125 |
C3—H3···O7i | 0.95 | 2.55 | 3.265 (3) | 133 |
C6—H6A···O3ii | 0.99 | 2.58 | 3.259 (2) | 125 |
C11—H11···O8ii | 1.00 | 2.38 | 3.179 (3) | 137 |
C12—H12···O6iii | 1.00 | 2.40 | 3.236 (2) | 141 |
C17—H17B···O4ii | 0.99 | 2.57 | 3.291 (2) | 130 |
C23—H23···O13 | 0.95 | 2.43 | 3.162 (3) | 134 |
C25—H25···O5 | 0.95 | 2.31 | 3.164 (3) | 149 |
C26—H26···O7 | 0.95 | 2.50 | 3.269 (3) | 138 |
C28—H28B···O12iv | 0.99 | 2.57 | 3.225 (3) | 124 |
C34—H34···O15iv | 1.00 | 2.42 | 3.182 (2) | 132 |
C43—H43···O14 | 0.95 | 2.47 | 3.084 (3) | 122 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, y+1/2, −z+1/2; (iii) x, −y+3/2, z+1/2; (iv) −x+1, y+1/2, −z+1/2. |
Acknowledgements
Financial support by the National Science Foundation (CHE1412909 and MRI1229426) is gratefully acknowledged.
Funding information
Funding for this research was provided by: NSF (grant No. 1412909/CHE to E.V. Rybak-Akimova; grant No. 1229426/MRI to A.Utz).
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