Improved syntheses, and structural and electronic characterization of carboxamide-substituted Tp^CONHPh,Me and Tp^CONHt-Bu,Me ligands

Improvements in the syntheses of the carboxamide-substituted tris­(pyrazol­yl)borate ligands Tp^CONHPh,Me [tris­(3-anilino­carbonyl-5-methyl­pyrazol-1-yl)borate] and Tp^CONHt-Bu,Me [tris­(3-tert-butyl­amino­carbonyl-5-methyl­pyrazol-1-yl)borate] are reported. Their Tl^I salts, namely [tris­(3-anilino­carbonyl-5-methyl­pyrazol-1-yl-κN²)borato]thallium(I), [Tl(C₃₃H₃₁BN₉O₃)], (II), and [tris­(3-tert-butyl­amino­carbonyl-5-methyl­pyrazol-1-yl-κN²)borato]thallium(I), [Tl(C₂₇H₄₃BN₉O₃)], (III), as well as the Cu^I carbonyl complexes (Tp^CONHPh,Me)Cu(CO), namely carbonyl[tris­(3-anilino­carbonyl-5-methyl­pyrazol-1-yl-κN²)borato]cop­per(I) tetra­hydro­furan tri­solvate, [Cu(C₃₃H₃₁BN₉O₃)(CO)]·3C₄H₈O, (IV), and (Tp^CONHt-Bu,Me)Cu(CO), namely carbon­yl[tris­(3-tert-butyl­amino­carbonyl-5-methyl­pyrazol-1-yl-κN²)borato]copper(I) tetra­hydro­furan hemi­solvate, [Cu(C₂₇H₄₃BN₉O₃)(CO)]·0.5C₄H₈O, (V), have been prepared. Their spectroscopic properties and structures are compared with those of related compounds. The mol­ecules of (II)–(V) show hydrogen bonding to either solvent mol­ecules or neighboring complex mol­ecules via amide groups. The title compounds feature the ability to engage other ligands in hydrogen bonding and they show strong electron-withdrawing character. Compound (V) displays voids of ca 800 ų in the crystal structure.

S1.

Over the past half century, tris­(pyrazolyl)borate (Tp) ligands or `scorpionates' have enjoyed a rich history in inorganic and coordination chemistry. Their popularity is due, in part, to their ease of preparation and the ability to stabilize a wide range of metal complexes via facile tuning of both steric and electronic properties of these monoanionic nitro­gen tripods (Trofimenko, 1999; Pettinari, 2008). In our laboratory, we have employed sterically bulky scorpionates (e.g. Tp^tBu,Me and Tp^iPr,Me), inter alia, in attempts to activate di­oxy­gen and isolate elusive terminal metal–oxo complexes. The characterization and isolation of these highly reactive species has proved challenging and often led to the isolation of products of C—H activation (Egan et al., 1990; Reinaud & Theopold, 1994; Thyagarajan et al., 2001; Qin et al., 2002a,b). Borovik and co-workers have had notable success stabilizing terminal transition metal–oxo species using ligands that have the ability to stabilize the oxo ligand through hydrogen-bonding inter­actions (Borovik, 2005; Taguchi et al., 2012). The success of these ligands led us to contemplate the chemistry of tris­(pyrazolyl)borates, with similar hydrogen-bonding ability. A review of the scorpionate literature reveals some tris­(pyrazolyl)borate ligands which have been functionalized with carboxamide substituents. Unfortunately, the syntheses reported for these ligands suffered from impurities and low yields (Olmo et al., 2006). Low-yielding ligand preparations are unsustainable, especially in cases where the preparation of the parent pyrazole involves nontrivial multistep syntheses. Trofimenko and co-workers reported a similar ligand system in which a high-boiling solvent was utilized (Rheingold et al., 2000). Presented here is an eminently practical adaptation for the synthesis of sterically hindered carboxamide-substituted tris­(pyrazolyl)borate ligands.

S2.

The reaction of 3.5 equivalents of the appropriate pyrazole with potassium borohydride in anisole at reflux (see Scheme 1) led to the isolation of Tp^CONHPh,MeTl, (II), and Tp^CONHt-Bu,MeTl, (III), in high yields (see Scheme 2). The previously reported synthesis of (I) employed a pyrazole melt, which led to thermal decomposition of the pyrazole and which, in turn, resulted in poor yield. Presumably, the use of a solvent with a boiling point lower than the melting point of the pyrazole circumvents its thermal decomposition. The low solubility of potassium salt (I) in anisole facilitated its isolation in high yield and purity. Compound (I) could then easily be converted into the corresponding Tl salt (II) through salt metathesis with Tl₂SO₄. Similarly, the previously reported synthesis of Tp^CONHt-Bu,MeK yielded an impure mixture containing unreacted pyrazole (Olmo et al., 2006). Since both Tp^CONHt-Bu,MeK and the free pyrazole have similar solubilities, purification by fractional crystallization proved difficult. Metathesis of the crude K salt mixture to yield the Tl salt, which has significantly lower solubility, affords clean separation of (III) from excess pyrazole.

The X-ray structures of (II) and (III) (Figs. 1 and 2; Table 1) feature trigonal–pyramidal coordination of Tl, which is typical of TlTp complexes (Trofimenko, 1999; Pettinari, 2008). The average Tl—N bond distances of 2.696 (3) Å for (II) and 2.684 (3) Å for (III) are substanti­ally longer than the corresponding average in TpTl complexes (2.59 Å; King et al., 2009). Although one Tl—N bond is significantly shorter in each of these compounds, this is most likely an effect of packing forces, since the pyrazole groups are equivalent in solution, as shown by ¹H NMR. Compared with the average N—Tl—N bond angle in TlTp complexes [75.1°; Cambridge Structural Database (CSD), Version 5.34, updated November 2012 (Allen, 2002)], the average N—Tl—N angles of complexes (II) and (III) of 69.75 (8) and 71.64 (8)°, respectively, are slightly more acute (Tables 2 and 3) (Janiak, 1997). These trends in the structural parameters are consistent with the lesser electron-donor strength of the carboxamide-substituted ligand.

With synthons (II) and (III) in hand, we prepared the copper(I) carbonyl complexes to elucidate the electron-donating ability of these ligands. The copper(I) complexes Tp^CONHPh,MeCu(CO), (IV), and Tp^CONHt-Bu,MeCu(CO), (V), were prepared by reacting (II) or (III) with Cu^I halide in tetra­hydro­furan (THF) under an atmosphere of CO (see Scheme 3). Compounds (IV) and (V) (see Scheme 4) were isolated after recrystallization at 243 K. Their ¹H NMR spectra are consistent with diamagnetic Tp^CONHR,Me complexes of monovalent copper (d¹⁰). The X-ray structure determinations of (IV) and (V) (Figs. 3 and 4) reveal distorted tetra­hedral coordination of copper. The Tp^CONHR,Me ligand is bonded symmetrically to the metal center. The carbonyl ligand sits inside the pocket created by the carboxamide substituents. The average Cu—C—O angles for (IV) and (V) [178.3 (3) and 174.4 (4)°, respectively] are consistent with the expected linear bonding of the CO ligand to Cu (Tables 4 and 5). The structural features are quite similar to those of previously reported TpCu(CO) complexes in the CSD. The CO stretching frequencies of (IV) and (V) [2092 and 2088 cm^-1, respectively] provide evidence for rather weak π-backbonding from the Cu^I center to CO. Table 6 shows a series of CO stretching frequencies for various Tp^R1,R2Cu(CO) complexes. The stretching frequencies of (IV) and (V) are close to that of Tp^Ph,PhCu(CO), and only slightly below those of perfluoralkyl-substituted species.

Although all of the compounds were crystallized in a similar fashion from THF, only (IV) displays hydrogen bonding to cocrystallized solvent molecules (Table 7). The crystal structure of (IV) reveals one molecule of THF hydrogen-bonded to the N—H group of each of the carboxamide groups. Each symmetry-unique entity, consisting of the compound molecule and three associated THF molecules, is isolated and does not participate in an extended hydrogen-bonded network. In (III) and (V), the compound molecules are hydrogen-bonded via N—H···O═C carboxamide groups to symmetry-generated equivalent molecules (Table 8; [No H-bond data provided for (V)]). In addition, (V) displays two void spaces, one of which is occupied by a non-hydrogen-bonded THF molecule. A second larger void of 827 ų, which appears to be vacant, suggests the potential of similar Tp ligands for host–guest chemistry (Inokuma et al., 2013; Huang et al., 2010).

S3.

The synthesis of sterically hindered carboxamide-substituted tris­(pyrazolyl)borate ligands has been optimized. By preparing these ligands in the presence of a high-boiling solvent, the Tl^I salts of Tp^CONHPh,Me and Tp^CONHt-Bu,Me can be isolated in high yields and purity. Their Cu^I carbonyl complexes can readily be obtained through salt metathesis of the ligand with Cu halides in the presence of CO. The CO stretching frequencies of the latter reveal the strong electron-withdrawing character of these ligands. The solid-state structures reveal the propensity of these ligands to form hydrogen bonds. The di­oxy­gen chemistry of the first-row transition metal complexes of these ligands is currently under investigation in this laboratory.

Related literature

For related literature, see: Allen (2002); Borovik (2005); Claramunt et al. (2005); Egan, Haggerty, Rheingold, Sendlinger & Theopold (1990); Huang et al. (2010); Inokuma et al. (2013); Janiak (1997); King et al. (2009); Musante (1945); Olmo et al. (2006); Pettinari (2008); Qin et al. (2002a, 2002b); Reinaud & Theopold (1994); Rheingold et al. (2000); Taguchi et al. (2012); Thyagarajan et al. (2001); Trofimenko (1999).

S4. Experimental

All reactions were carried out under a nitrogen atmosphere. All solvents were dried and distilled from appropriate drying agents under an atmosphere of nitrogen. 3-Anilinocarbonyl-5-methylpyrazole and 3-tert-butylaminocarbonyl-5-methylpyrazole were synthesized using a modified procedure (Claramunt et al., 2005; Musante, 1945; Rheingold et al., 2000). The pyrazole and tris(pyrazolyl)borate complexes were manipulated as solids in a Vacuum Atmospheres dry-box under nitrogen. ¹H NMR spectra were obtained on Bruker AV-400 spectrometer and were referenced to the residual ¹H signal of the deuterated solvent. FT–IR spectra (KBR pellets) were recorded on a Mattson Alpha Centauri spectrometer at 4 cm^-1 resolution.

4.1 Preparation of Tp^CONHPh,MeK, (I)

In a dry box, a 250 ml Schlenk flask was charged with 3-anilinocarbonyl-5-methylpyrazole (22 g, 0.11 mol), potassium borohydride (1.7 g, 0.031 mol) and anisole (125 ml) and fitted with a reflux condenser. The apparatus was attached to a Schlenk line and purged with nitrogen. The mixture was allowed to reflux for 24 h, over which time a colourless precipitate was obtained. The mixture was filtered hot, washed with several portions of hot anisole and dried under vacuum. The solid was placed in a 250 ml round-bottomed flask with acetonitrile (100 ml). The mixture was refluxed for 1 h to remove any unreacted pyrazole. The solution was filtered and washed with several portions of hot acetonitrile followed by several portions of diethyl ether, and dried in vacuo (yield 15 g, 73%). Characterization was consistent with reported literature values (Olmo et al., 2006).

4.2 Preparation of Tp^CONHPh,MeTl, (II)

In a 500 ml round-bottomed flask equipped with a stirrer bar, (I) (5 g) was dissolved in a mixture of THF and dimethylformamide (150 ml, 10:1 v/v). An aqueous solution of thallium sulfate (2.5 g, 4.95 mmol) was added and the solution was stirred for 1 h, during which time a white precipitate formed. To complete precipitation of the product, distilled water (100 ml) was added to the solution and stirring was continued for an additional 15 min. The product was collected on a frit, washed with copious amounts of water and dried with gentle heating under vacuum, yielding the desired product (yield 3.9 g, 62%; m.p. 555 K). ¹H NMR (d₆-DMSO, δ, p.p.m.): 9.96 (s, 3H, NH), 7.74 (m, 6H, phenyl H), 7.33 (m, 6H, phenyl H), 7.08 (m, 3H, phenyl H), 6.81 (s, 3H, pz H), 2.47 (s, 9H, methyl H). IR (KBr, ν, cm^-1): 3302 (NH), 2505 (BH), 1653 (CO).

4.3 Preparation of Tp^CONHt-Bu,MeTl, (III)

In a dry box, a 250 ml Schlenk flask was charged with 3-tert-butylaminocarbonyl-5-methylpyrazole (18 g, 0.1 mol), potassium borohydride (1.5 g, 0.03 mol) and anisole (110 ml) and fitted with a reflux condenser. The apparatus was attached to a Schlenk line and purged with nitrogen and the mixture was allowed to reflux for 24 h. The solvent was stripped and the residue dissolved in a minimum amount of THF. An aqueous solution of thallium sulfate (8.5 g, 0.016 mol) was added slowly and the mixture was stirred for 1 h. The product was extracted into dichloromethane and dried over sodium sulfate. After removal of the solvent, the residue was triturated with methanol until a colourless solid was obtained. The solid was collected on a frit, washed with several portions of methanol and dried in vacuo (yield 13.4 g, 63%; m.p. 534 K). ¹H NMR (CDCl₃, δ, p.p.m.): 6.19 (s, 3H, pz H), 2.37 (s, 9H, methyl H), 1.41 (s, 18H, t-butyl H). IR (KBr, ν, cm^-1): 3327 (NH), 2530 (BH), 1649 (CO).

4.4 Preparation of Tp^CONHPh,MeCu(CO), (IV)

In a dry box, an ampoule equipped with a stirrer bar was charged with (II) (0.5 g, 0.61 mmol), CuI (0.12 g, 0.63 mmol) and THF (20 ml). The mixture was subjected to three freeze/pump/thaw cycles and then exposed to 1 atm (1 atm = 101325 Pa) of carbon monoxide. The solution was stirred overnight. After three freeze/pump/thaw cycles to remove excess CO, the ampoule was brought back into the dry box and the mixture filtered through a plug of Celite. After the solvent had been concentrated to 10 ml, the solution was placed in the freezer at 243 K and left overnight. The crystals which formed were collected on a frit, washed with pentane (10 ml) and dried under vacuum (yield 0.33 g, 76%; m.p. 520 K). ¹H NMR (CD₂Cl₂, δ, p.p.m.): 7.96 (s, 3H, NH), 7.58 (m, 6H, phenyl H), 7.27 (m, 6H, phenyl H), 7.05 (m, 3H, phenyl H), 6.36 (s, 3H, pz H), 2.41 (s, 9H, methyl H). IR (KBr, ν, cm^-1): 3305 (NH), 2549 (BH), 2092 (Cu—CO), 1665 (L—CO).

4.5 Preparation of Tp^CONHt-Bu,MeCu(CO), (V)

Compound (V) was synthesized in an analogous manner to (IV), using (III) (0.5 g, 0.66 mmol) and CuBr (0.104 g, 0.727 mmol) (yield 0.35 g, 86%; m.p. 493 K). ¹H NMR (d₈-THF, δ, p.p.m.): 6.28 (s, 3H, pz H), 2.42 (s, 9H, methyl H), 1.46 (s, 18H, t-butyl H). IR (KBr, ν, cm^-1): 3388 (NH), 2532 (BH), 2088 (Cu—CO), 1668 (L—CO).

S5. Refinement

Two symmetry-unique but chemically identical compound molecules are located in the asymmetric units of (IV) and (V). Each compound molecule in (IV) has three associated THF solvent molecules, each hydrogen-bonded to the carboxamide H atoms.

The threefold axis in (V) affords chirality. However, these crystals were obtained from a racemic solution, therefore suggesting that both enantiomers are accessible from spontaneous resolution during crystallization. A severely disordered THF molecule was found in the smaller of two hydrophobic voids formed by the pyrazole arms of the Tp ligand in (V). The THF O atom was assigned by a comparison of the isotropic parameters in the initially observed five-membered ring. Two disordered positions were found with refined site occupancies of 0.60:0.40, with chemically equivalent atom positions constrained with equal atomic displacement parameters, and with 1,2 and 1,3 distances restrained to be equal. All THF molecules were treated with rigid-bond anisotropic constraints. The disordered THF, clearly not hydrogen-bonded, was given `anti-bumping' restraints to avoid close approaches to the compound molecule.

In addition to distance restraints for the treatment of disordered solvent in (V), rigid-bond and similarity restraints had to employed to ensure physically reasonable anisotropic displacement parameters; a total of 252, 95 and 195 restraints were used in the refinements of (III), (IV) and (V), respectively.

A second larger void was found in (V), with a volume of 827 ų centered at (0, 3/4, 1/2), with no residual electron density that could be modeled as a molecule.

The H atoms of the carboxamide groups involved in hydrogen bonding in (IV) were located from a difference map and restrained to equal N—H distances. The hydride ligands of the B atoms were located from a difference map. All other H atoms were placed in calculated positions. For all H atoms, U_iso(H) = 1.2U_eq(parent), or 1.5U_eq(C) for methyl H atoms.

During the final steps of the refinements, two [for (III)], three [for (IV)] and 19 [for (V)] reflections, wherein the differences between the observed and calculated intensities were greater than 10 or the calculated structure factors were greater than 0.80 of the maximum calculated structure factor, were considered as outliers and were omitted. The outliers for (III) and (IV) were reflections that were most likely affected by the beam-stop shadow. We cannot discount the possibility of a minor secondary crystal causing the 19 outlier reflections in (V).

Computing details

For all compounds, data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: APEX2 (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: APEX2 (Bruker, 2007); software used to prepare material for publication: APEX2 (Bruker, 2007).

Figures

Fig. 1. The syntheses of (a) (Tp^CONHR,Me)Tl ligands and (b) (Tp^CONHR,Me)- Cu(CO) complexes.

Fig. 2. The molecular structure of Tp^CONHPh,MeTl, (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. C-bound H atoms have been omitted for clarity.

Fig. 3. The molecular structure of Tp^CONHt-Bu,MeTl, (III), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. C-bound H atoms have been omitted for clarity.

Fig. 4. The molecular structure of Tp^CONHPh,MeCu(CO), (IV), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen-bond interactions are shown as dashed lines. A representative molecular assembly is depicted. C-bound H atoms have been omitted for clarity.

Fig. 5. The molecular structure of Tp^CONHt-Bu,MeCu(CO), (V), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. A representative molecule is depicted. C-bound H atoms have been omitted for clarity.

(II) [Tris(3-anilinocarbonyl-5-methylpyrazol-1-yl-κN²)borato]thallium(I)

Crystal data

[Tl(C33H31BN9O3)]	Dx = 1.652 Mg m^−3
Mr = 816.85	Cu Kα radiation, λ = 1.54178 Å
Tetragonal, I41/a	Cell parameters from 9853 reflections
Hall symbol: -I 4ad	θ = 3.4–69.2°
a = 30.2283 (4) Å	µ = 9.85 mm^−1
c = 14.3753 (3) Å	T = 200 K
V = 13135.4 (4) Å^3	Block, colourless
Z = 16	0.17 × 0.07 × 0.04 mm
F(000) = 6432

Data collection

Bruker APEXII area-detector diffractometer	6060 independent reflections
Radiation source: fine-focus sealed tube	5178 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 1672 pixels mm^-1	θmax = 70.1°, θmin = 2.9°
ϕ and ω scans	h = −35→36
Absorption correction: numerical (APEX2; Bruker, 2007)	k = −34→35
Tmin = 0.285, Tmax = 0.677	l = −16→15
48743 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.040P)^2 + 20.0316P] where P = (Fo^2 + 2Fc^2)/3
6060 reflections	(Δ/σ)max = 0.001
430 parameters	Δρmax = 0.63 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

Special details

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.

Data crystals were selected, sectioned if necessary, mounted on plastic mesh with viscous oil and cooled to 200 K. Diffraction data were collected on a Bruker APEXII DUO diffractometer, using Cu Kα radiation focused with Göbel mirrors.

Data were corrected for absorption using numerical methods, and the structure was solved using direct methods and refined using full-matrix least-squares based on F² with atomic scattering factors contained in the SHELX program suite (Sheldrick, 2008).

Systematic absences, equivalent reflections and unit-cell parameters were uniquely consistent with space groups I4₁/a for (II).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Tl1	0.089262 (4)	0.030051 (5)	0.812419 (10)	0.04232 (6)
B1	0.11375 (12)	−0.04395 (13)	1.0201 (3)	0.0376 (8)
H1B	0.1198 (12)	−0.0642 (12)	1.076 (3)	0.045*
N1	0.06602 (8)	0.02139 (9)	0.98387 (19)	0.0370 (6)
N2	0.07291 (9)	−0.01435 (9)	1.03899 (19)	0.0372 (6)
N3	−0.01100 (9)	0.10985 (9)	1.0164 (2)	0.0405 (6)
H3A	−0.0243	0.0967	1.0633	0.049*
N4	0.15743 (8)	0.01246 (9)	0.93067 (19)	0.0366 (6)
N5	0.15378 (9)	−0.01245 (9)	1.00909 (19)	0.0374 (6)
N6	0.24768 (10)	0.08560 (9)	0.8791 (2)	0.0453 (7)
H6A	0.2607	0.0802	0.9326	0.054*
N7	0.08317 (9)	−0.05946 (9)	0.8579 (2)	0.0408 (6)
N8	0.11074 (9)	−0.07068 (9)	0.92846 (19)	0.0383 (6)
N9	0.08062 (10)	−0.11170 (10)	0.6325 (2)	0.0470 (7)
H9A	0.1026	−0.1295	0.6471	0.056*
O1	0.04695 (8)	0.10330 (8)	0.91594 (18)	0.0485 (6)
O2	0.18486 (9)	0.07146 (9)	0.79540 (19)	0.0525 (6)
O3	0.04069 (11)	−0.05363 (11)	0.6891 (2)	0.0695 (9)
C1	0.03617 (10)	0.04657 (10)	1.0272 (2)	0.0350 (7)
C2	0.02355 (10)	0.02717 (11)	1.1116 (2)	0.0377 (7)
H2A	0.0028	0.0382	1.1554	0.045*
C3	0.04755 (10)	−0.01125 (11)	1.1175 (2)	0.0376 (7)
C4	0.02454 (10)	0.08883 (11)	0.9811 (2)	0.0375 (7)
C5	−0.02387 (16)	0.16795 (14)	0.8996 (3)	0.0638 (11)
H5A	−0.0055	0.1532	0.8559	0.077*
C6	−0.04486 (19)	0.20688 (16)	0.8751 (4)	0.0809 (15)
H6B	−0.0405	0.2187	0.8146	0.097*
C7	−0.0712 (2)	0.22821 (18)	0.9349 (5)	0.103 (2)
H7A	−0.0848	0.2553	0.9179	0.123*
C8	−0.0781 (3)	0.2102 (2)	1.0211 (5)	0.131 (3)
H8A	−0.0975	0.2246	1.0635	0.157*
C9	−0.0572 (2)	0.17129 (17)	1.0474 (4)	0.095 (2)
H9B	−0.0622	0.1592	1.1074	0.114*
C10	−0.02955 (12)	0.15057 (11)	0.9870 (3)	0.0460 (8)
C11	0.04860 (13)	−0.04468 (13)	1.1939 (3)	0.0500 (9)
H11A	0.0425	−0.0741	1.1682	0.075*
H11B	0.0261	−0.0373	1.2404	0.075*
H11C	0.0779	−0.0446	1.2231	0.075*
C12	0.19287 (11)	0.03807 (11)	0.9436 (2)	0.0393 (7)
C13	0.21216 (13)	0.02943 (13)	1.0291 (3)	0.0552 (10)
H13A	0.2378	0.0430	1.0543	0.066*
C14	0.18666 (13)	−0.00282 (13)	1.0700 (3)	0.0501 (9)
C15	0.20721 (11)	0.06687 (11)	0.8662 (3)	0.0409 (8)
C16	0.25063 (15)	0.13869 (13)	0.7493 (3)	0.0616 (11)
H16A	0.2194	0.1381	0.7428	0.074*
C17	0.27599 (19)	0.16527 (16)	0.6925 (4)	0.0779 (15)
H17A	0.2618	0.1832	0.6473	0.093*
C18	0.32088 (19)	0.16646 (17)	0.6997 (4)	0.0791 (16)
H18A	0.3378	0.1848	0.6595	0.095*
C19	0.34159 (16)	0.14077 (18)	0.7659 (4)	0.0757 (14)
H19A	0.3729	0.1412	0.7710	0.091*
C20	0.31672 (14)	0.11426 (15)	0.8251 (3)	0.0594 (10)
H20A	0.3310	0.0971	0.8717	0.071*
C21	0.27125 (13)	0.11286 (12)	0.8162 (3)	0.0485 (9)
C22	0.19221 (18)	−0.02686 (18)	1.1605 (3)	0.0782 (15)
H22A	0.1924	−0.0588	1.1490	0.117*
H22B	0.1676	−0.0194	1.2020	0.117*
H22C	0.2202	−0.0180	1.1894	0.117*
C23	0.09449 (11)	−0.08579 (11)	0.7862 (2)	0.0390 (7)
C24	0.12987 (14)	−0.11300 (12)	0.8104 (3)	0.0533 (9)
H24A	0.1442	−0.1343	0.7722	0.064*
C25	0.13952 (13)	−0.10260 (12)	0.9008 (3)	0.0508 (9)
C26	0.06914 (12)	−0.08172 (12)	0.6987 (3)	0.0452 (8)
C27	0.03142 (14)	−0.08942 (15)	0.5052 (3)	0.0576 (10)
H27A	0.0224	−0.0637	0.5381	0.069*
C28	0.01393 (16)	−0.09884 (18)	0.4170 (3)	0.0702 (12)
H28A	−0.0073	−0.0795	0.3900	0.084*
C29	0.02733 (17)	−0.13584 (18)	0.3698 (3)	0.0732 (13)
H29A	0.0154	−0.1420	0.3100	0.088*
C30	0.05773 (18)	−0.16406 (18)	0.4077 (3)	0.0746 (13)
H30A	0.0668	−0.1897	0.3745	0.089*
C31	0.07520 (15)	−0.15520 (15)	0.4942 (3)	0.0614 (11)
H31A	0.0965	−0.1747	0.5204	0.074*
C32	0.06195 (12)	−0.11808 (13)	0.5434 (3)	0.0485 (9)
C33	0.17423 (18)	−0.12110 (17)	0.9639 (4)	0.0829 (16)
H33A	0.1904	−0.0968	0.9936	0.124*
H33B	0.1949	−0.1392	0.9277	0.124*
H33C	0.1602	−0.1394	1.0118	0.124*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Tl1	0.04329 (9)	0.05036 (9)	0.03332 (9)	0.00415 (5)	0.00269 (6)	−0.00045 (6)
B1	0.0391 (19)	0.0412 (19)	0.033 (2)	0.0024 (15)	−0.0019 (15)	−0.0050 (16)
N1	0.0355 (13)	0.0420 (14)	0.0334 (15)	0.0009 (11)	0.0003 (11)	−0.0012 (12)
N2	0.0385 (14)	0.0387 (14)	0.0344 (15)	−0.0007 (11)	−0.0009 (11)	−0.0032 (11)
N3	0.0396 (14)	0.0383 (14)	0.0436 (17)	0.0000 (11)	0.0069 (12)	0.0018 (12)
N4	0.0353 (13)	0.0414 (14)	0.0331 (15)	0.0014 (11)	−0.0003 (11)	−0.0032 (11)
N5	0.0385 (14)	0.0421 (14)	0.0316 (15)	0.0010 (11)	−0.0029 (11)	−0.0033 (12)
N6	0.0464 (16)	0.0449 (15)	0.0447 (18)	−0.0062 (12)	−0.0003 (13)	−0.0056 (13)
N7	0.0382 (14)	0.0476 (16)	0.0365 (16)	0.0043 (12)	0.0002 (12)	−0.0057 (13)
N8	0.0386 (14)	0.0380 (14)	0.0384 (16)	−0.0009 (11)	0.0004 (12)	−0.0067 (12)
N9	0.0414 (15)	0.0611 (19)	0.0386 (17)	0.0010 (13)	0.0013 (13)	−0.0111 (14)
O1	0.0459 (13)	0.0515 (14)	0.0480 (15)	0.0038 (11)	0.0121 (11)	0.0071 (11)
O2	0.0534 (15)	0.0544 (15)	0.0497 (16)	−0.0088 (12)	−0.0079 (12)	0.0048 (12)
O3	0.078 (2)	0.086 (2)	0.0451 (17)	0.0327 (17)	−0.0100 (14)	−0.0140 (15)
C1	0.0317 (15)	0.0386 (16)	0.0347 (17)	−0.0029 (12)	0.0006 (13)	−0.0057 (13)
C2	0.0339 (15)	0.0446 (17)	0.0346 (18)	−0.0045 (13)	0.0047 (13)	−0.0052 (14)
C3	0.0367 (16)	0.0459 (18)	0.0301 (17)	−0.0071 (13)	−0.0010 (13)	−0.0053 (14)
C4	0.0346 (16)	0.0417 (17)	0.0362 (18)	−0.0050 (13)	0.0012 (14)	−0.0054 (14)
C5	0.083 (3)	0.057 (2)	0.051 (3)	0.018 (2)	0.001 (2)	0.000 (2)
C6	0.103 (4)	0.068 (3)	0.072 (3)	0.022 (3)	−0.002 (3)	0.017 (3)
C7	0.127 (5)	0.068 (3)	0.114 (5)	0.051 (3)	0.025 (4)	0.028 (3)
C8	0.175 (7)	0.088 (4)	0.131 (6)	0.077 (5)	0.075 (5)	0.033 (4)
C9	0.125 (5)	0.071 (3)	0.089 (4)	0.047 (3)	0.054 (4)	0.026 (3)
C10	0.0448 (18)	0.0401 (18)	0.053 (2)	0.0007 (14)	0.0052 (16)	−0.0010 (16)
C11	0.058 (2)	0.053 (2)	0.039 (2)	−0.0027 (17)	0.0040 (17)	0.0032 (16)
C12	0.0379 (16)	0.0415 (17)	0.0386 (19)	−0.0010 (13)	−0.0024 (14)	−0.0101 (14)
C13	0.054 (2)	0.061 (2)	0.051 (2)	−0.0173 (18)	−0.0168 (18)	−0.0039 (19)
C14	0.053 (2)	0.056 (2)	0.041 (2)	−0.0068 (17)	−0.0110 (17)	−0.0011 (17)
C15	0.0428 (17)	0.0364 (16)	0.044 (2)	−0.0015 (13)	−0.0011 (15)	−0.0092 (14)
C16	0.067 (3)	0.052 (2)	0.066 (3)	−0.0060 (19)	0.002 (2)	0.000 (2)
C17	0.105 (4)	0.061 (3)	0.067 (4)	−0.021 (3)	0.003 (3)	0.006 (2)
C18	0.100 (4)	0.076 (3)	0.062 (3)	−0.042 (3)	0.023 (3)	−0.010 (3)
C19	0.065 (3)	0.094 (4)	0.068 (3)	−0.036 (3)	0.014 (2)	−0.021 (3)
C20	0.056 (2)	0.068 (3)	0.054 (3)	−0.0166 (19)	0.0016 (19)	−0.013 (2)
C21	0.055 (2)	0.0455 (19)	0.045 (2)	−0.0112 (16)	0.0093 (17)	−0.0150 (16)
C22	0.089 (3)	0.093 (4)	0.052 (3)	−0.028 (3)	−0.033 (2)	0.018 (2)
C23	0.0400 (17)	0.0407 (17)	0.0363 (18)	−0.0048 (13)	0.0041 (14)	−0.0070 (14)
C24	0.066 (2)	0.0453 (19)	0.048 (2)	0.0138 (17)	−0.0027 (19)	−0.0132 (17)
C25	0.058 (2)	0.0454 (19)	0.049 (2)	0.0113 (16)	−0.0047 (18)	−0.0097 (17)
C26	0.0434 (18)	0.055 (2)	0.037 (2)	−0.0015 (16)	0.0030 (15)	−0.0076 (16)
C27	0.062 (2)	0.072 (3)	0.039 (2)	−0.002 (2)	0.0038 (18)	−0.0052 (19)
C28	0.066 (3)	0.098 (4)	0.046 (3)	0.001 (2)	−0.001 (2)	0.004 (2)
C29	0.083 (3)	0.103 (4)	0.033 (2)	−0.019 (3)	0.000 (2)	−0.010 (2)
C30	0.087 (3)	0.087 (3)	0.049 (3)	−0.001 (3)	−0.002 (2)	−0.021 (2)
C31	0.071 (3)	0.068 (3)	0.045 (2)	0.002 (2)	−0.001 (2)	−0.014 (2)
C32	0.0443 (19)	0.064 (2)	0.037 (2)	−0.0097 (16)	0.0067 (15)	−0.0040 (17)
C33	0.098 (4)	0.082 (3)	0.068 (3)	0.047 (3)	−0.024 (3)	−0.023 (3)

Geometric parameters (Å, º)

Tl1—N1	2.576 (3)	C9—H9B	0.9500
Tl1—N4	2.724 (3)	C11—H11A	0.9800
Tl1—N7	2.790 (3)	C11—H11B	0.9800
B1—N5	1.548 (5)	C11—H11C	0.9800
B1—N8	1.548 (4)	C12—C13	1.384 (5)
B1—N2	1.549 (4)	C12—C15	1.478 (5)
B1—H1B	1.03 (4)	C13—C14	1.375 (5)
N1—C1	1.335 (4)	C13—H13A	0.9500
N1—N2	1.356 (4)	C14—C22	1.500 (6)
N2—C3	1.368 (4)	C16—C17	1.378 (6)
N3—C4	1.347 (4)	C16—C21	1.386 (6)
N3—C10	1.417 (4)	C16—H16A	0.9500
N3—H3A	0.8800	C17—C18	1.361 (8)
N4—C12	1.335 (4)	C17—H17A	0.9500
N4—N5	1.360 (4)	C18—C19	1.378 (8)
N5—C14	1.356 (4)	C18—H18A	0.9500
N6—C15	1.361 (4)	C19—C20	1.390 (6)
N6—C21	1.416 (5)	C19—H19A	0.9500
N6—H6A	0.8800	C20—C21	1.381 (6)
N7—C23	1.346 (4)	C20—H20A	0.9500
N7—N8	1.356 (4)	C22—H22A	0.9800
N8—C25	1.359 (4)	C22—H22B	0.9800
N9—C26	1.359 (4)	C22—H22C	0.9800
N9—C32	1.413 (5)	C23—C24	1.393 (5)
N9—H9A	0.8800	C23—C26	1.478 (5)
O1—C4	1.236 (4)	C24—C25	1.368 (5)
O2—C15	1.230 (4)	C24—H24A	0.9500
O3—C26	1.217 (5)	C25—C33	1.496 (6)
C1—C2	1.400 (5)	C27—C32	1.380 (6)
C1—C4	1.482 (5)	C27—C28	1.403 (6)
C2—C3	1.372 (5)	C27—H27A	0.9500
C2—H2A	0.9500	C28—C29	1.369 (7)
C3—C11	1.492 (5)	C28—H28A	0.9500
C5—C10	1.373 (6)	C29—C30	1.367 (7)
C5—C6	1.382 (6)	C29—H29A	0.9500
C5—H5A	0.9500	C30—C31	1.377 (6)
C6—C7	1.337 (7)	C30—H30A	0.9500
C6—H6B	0.9500	C31—C32	1.385 (5)
C7—C8	1.369 (8)	C31—H31A	0.9500
C7—H7A	0.9500	C33—H33A	0.9800
C8—C9	1.388 (7)	C33—H33B	0.9800
C8—H8A	0.9500	C33—H33C	0.9800
C9—C10	1.358 (6)
N1—Tl1—N4	65.76 (8)	N4—C12—C13	110.6 (3)
N1—Tl1—N7	70.08 (8)	N4—C12—C15	118.2 (3)
N4—Tl1—N7	73.40 (8)	C13—C12—C15	131.0 (3)
N5—B1—N8	106.3 (3)	C14—C13—C12	106.1 (3)
N5—B1—N2	106.6 (3)	C14—C13—H13A	127.0
N8—B1—N2	113.8 (3)	C12—C13—H13A	127.0
N5—B1—H1B	108 (2)	N5—C14—C13	106.7 (3)
N8—B1—H1B	111 (2)	N5—C14—C22	122.5 (3)
N2—B1—H1B	110 (2)	C13—C14—C22	130.7 (4)
C1—N1—N2	106.6 (3)	O2—C15—N6	124.0 (3)
C1—N1—Tl1	125.0 (2)	O2—C15—C12	121.9 (3)
N2—N1—Tl1	126.73 (19)	N6—C15—C12	114.0 (3)
N1—N2—C3	110.0 (3)	C17—C16—C21	119.3 (4)
N1—N2—B1	118.7 (3)	C17—C16—H16A	120.4
C3—N2—B1	129.1 (3)	C21—C16—H16A	120.4
C4—N3—C10	127.8 (3)	C18—C17—C16	121.7 (5)
C4—N3—H3A	116.1	C18—C17—H17A	119.2
C10—N3—H3A	116.1	C16—C17—H17A	119.2
C12—N4—N5	105.7 (3)	C17—C18—C19	119.3 (4)
C12—N4—Tl1	125.5 (2)	C17—C18—H18A	120.3
N5—N4—Tl1	124.33 (18)	C19—C18—H18A	120.3
C14—N5—N4	110.9 (3)	C18—C19—C20	120.1 (5)
C14—N5—B1	129.7 (3)	C18—C19—H19A	119.9
N4—N5—B1	119.3 (3)	C20—C19—H19A	119.9
C15—N6—C21	127.4 (3)	C21—C20—C19	119.9 (5)
C15—N6—H6A	116.3	C21—C20—H20A	120.0
C21—N6—H6A	116.3	C19—C20—H20A	120.0
C23—N7—N8	105.6 (3)	C20—C21—C16	119.7 (4)
C23—N7—Tl1	112.2 (2)	C20—C21—N6	117.3 (4)
N8—N7—Tl1	112.17 (19)	C16—C21—N6	123.0 (4)
N7—N8—C25	110.6 (3)	C14—C22—H22A	109.5
N7—N8—B1	122.8 (3)	C14—C22—H22B	109.5
C25—N8—B1	125.6 (3)	H22A—C22—H22B	109.5
C26—N9—C32	128.6 (3)	C14—C22—H22C	109.5
C26—N9—H9A	115.7	H22A—C22—H22C	109.5
C32—N9—H9A	115.7	H22B—C22—H22C	109.5
N1—C1—C2	110.5 (3)	N7—C23—C24	110.7 (3)
N1—C1—C4	116.3 (3)	N7—C23—C26	118.1 (3)
C2—C1—C4	133.2 (3)	C24—C23—C26	131.2 (3)
C3—C2—C1	105.3 (3)	C25—C24—C23	105.3 (3)
C3—C2—H2A	127.3	C25—C24—H24A	127.3
C1—C2—H2A	127.3	C23—C24—H24A	127.3
N2—C3—C2	107.6 (3)	N8—C25—C24	107.7 (3)
N2—C3—C11	123.3 (3)	N8—C25—C33	122.5 (4)
C2—C3—C11	129.1 (3)	C24—C25—C33	129.8 (4)
O1—C4—N3	123.7 (3)	O3—C26—N9	124.5 (3)
O1—C4—C1	121.0 (3)	O3—C26—C23	121.4 (3)
N3—C4—C1	115.3 (3)	N9—C26—C23	114.1 (3)
C10—C5—C6	120.1 (4)	C32—C27—C28	119.0 (4)
C10—C5—H5A	120.0	C32—C27—H27A	120.5
C6—C5—H5A	120.0	C28—C27—H27A	120.5
C7—C6—C5	121.3 (5)	C29—C28—C27	120.1 (5)
C7—C6—H6B	119.3	C29—C28—H28A	119.9
C5—C6—H6B	119.3	C27—C28—H28A	119.9
C6—C7—C8	118.8 (5)	C30—C29—C28	120.7 (4)
C6—C7—H7A	120.6	C30—C29—H29A	119.6
C8—C7—H7A	120.6	C28—C29—H29A	119.6
C7—C8—C9	120.9 (5)	C29—C30—C31	119.8 (5)
C7—C8—H8A	119.6	C29—C30—H30A	120.1
C9—C8—H8A	119.6	C31—C30—H30A	120.1
C10—C9—C8	119.8 (5)	C30—C31—C32	120.5 (5)
C10—C9—H9B	120.1	C30—C31—H31A	119.7
C8—C9—H9B	120.1	C32—C31—H31A	119.7
C9—C10—C5	119.0 (4)	C27—C32—C31	119.9 (4)
C9—C10—N3	117.0 (4)	C27—C32—N9	122.9 (4)
C5—C10—N3	123.7 (3)	C31—C32—N9	117.2 (4)
C3—C11—H11A	109.5	C25—C33—H33A	109.5
C3—C11—H11B	109.5	C25—C33—H33B	109.5
H11A—C11—H11B	109.5	H33A—C33—H33B	109.5
C3—C11—H11C	109.5	C25—C33—H33C	109.5
H11A—C11—H11C	109.5	H33A—C33—H33C	109.5
H11B—C11—H11C	109.5	H33B—C33—H33C	109.5

(III) [Tris(3-tert-butylaminocarbonyl-5-methylpyrazol-1-yl-κN²)borato]thallium(I)

Crystal data

[Tl(C27H43BN9O3)]	F(000) = 1512
Mr = 756.88	Dx = 1.484 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4944 reflections
a = 11.6038 (5) Å	θ = 2.4–19.3°
b = 12.7036 (6) Å	µ = 4.81 mm^−1
c = 23.0839 (10) Å	T = 200 K
β = 95.2010 (8)°	Block, colourless
V = 3388.8 (3) Å^3	0.41 × 0.30 × 0.20 mm
Z = 4

Data collection

Bruker APEXII area-detector diffractometer	10043 independent reflections
Radiation source: fine-focus sealed tube	6330 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.071
Detector resolution: 1672 pixels mm^-1	θmax = 30.9°, θmin = 1.8°
ϕ and ω scans	h = −15→16
Absorption correction: multi-scan (APEX2; Bruker, 2007)	k = −17→17
Tmin = 0.243, Tmax = 0.445	l = −32→32
49674 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0191P)^2] where P = (Fo^2 + 2Fc^2)/3
10043 reflections	(Δ/σ)max = 0.001
394 parameters	Δρmax = 0.73 e Å^−3
252 restraints	Δρmin = −0.71 e Å^−3

Special details

Experimental. Data collection is performed with four batch runs at ϕ = 0.00° (600 frames), at ϕ = 90.00° (600 frames), at ϕ = 180° (600 frames) and at ϕ = 270° (600 frames). Frame width = 0.30° in ω.

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.

Data crystals were selected, sectioned if necessary, mounted on plastic mesh with viscous oil and cooled to 200 K. Diffraction data were collected on a Bruker APEXII DUO diffractometer, using Mo Kα radiation monochromated by graphite.

Data were corrected for absorption using multi-scan methods (Bruker, 2007), and the structure was solved using direct methods and refined using full-matrix least-squares based on F² with atomic scattering factors contained in the SHELX program suite (Sheldrick, 2008).

Systematic absences, equivalent reflections and unit-cell parameters were uniquely consistent with space group P2₁/n.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Tl1	0.019559 (12)	0.828989 (11)	0.124026 (6)	0.04374 (5)
B1	0.2032 (3)	0.6584 (3)	0.03652 (16)	0.0322 (8)
H1B	0.257 (3)	0.606 (2)	0.0107 (13)	0.039*
O1	−0.1274 (2)	0.97600 (18)	−0.07725 (10)	0.0460 (6)
O2	0.4165 (2)	0.8962 (2)	0.24147 (11)	0.0540 (7)
O3	−0.1574 (3)	0.6632 (2)	0.15868 (15)	0.0881 (11)
N1	0.0394 (2)	0.7883 (2)	0.00885 (11)	0.0334 (6)
N2	0.1376 (2)	0.73936 (19)	−0.00432 (11)	0.0312 (6)
N3	−0.1807 (3)	0.8709 (2)	−0.00499 (14)	0.0431 (8)
H3N	−0.159 (3)	0.827 (3)	0.0162 (16)	0.052*
N4	0.2514 (2)	0.79366 (19)	0.11689 (11)	0.0333 (6)
N5	0.2874 (2)	0.7150 (2)	0.08247 (11)	0.0328 (6)
N6	0.2594 (3)	0.9729 (3)	0.19216 (12)	0.0453 (8)
H6N	0.228 (3)	0.981 (3)	0.1637 (15)	0.054*
N7	0.0424 (2)	0.6325 (2)	0.10199 (12)	0.0384 (7)
N8	0.1169 (2)	0.5898 (2)	0.06660 (11)	0.0344 (6)
N9	−0.1339 (3)	0.4992 (2)	0.19701 (14)	0.0475 (8)
H9N	−0.083 (3)	0.458 (3)	0.2027 (16)	0.057*
C1	0.0057 (3)	0.8483 (2)	−0.03755 (14)	0.0325 (7)
C2	0.0821 (3)	0.8384 (3)	−0.08026 (14)	0.0406 (8)
H2A	0.0779	0.8728	−0.1169	0.049*
C3	0.1650 (3)	0.7683 (3)	−0.05828 (14)	0.0381 (8)
C4	0.2682 (3)	0.7267 (3)	−0.08481 (16)	0.0595 (11)
H4A	0.2629	0.6499	−0.0877	0.089*
H4B	0.3385	0.7462	−0.0605	0.089*
H4C	0.2709	0.7568	−0.1238	0.089*
C5	−0.1058 (3)	0.9056 (3)	−0.04150 (15)	0.0361 (8)
C6	−0.3040 (3)	0.8996 (3)	−0.00303 (18)	0.0492 (10)
C7	−0.3459 (4)	0.8432 (4)	0.0475 (3)	0.115 (2)
H7A	−0.3032	0.8680	0.0835	0.172*
H7B	−0.3336	0.7674	0.0433	0.172*
H7C	−0.4287	0.8571	0.0491	0.172*
C8	−0.3171 (4)	1.0172 (3)	0.0018 (2)	0.0895 (17)
H8A	−0.2826	1.0408	0.0399	0.134*
H8B	−0.3994	1.0357	−0.0025	0.134*
H8C	−0.2778	1.0517	−0.0289	0.134*
C9	−0.3705 (4)	0.8612 (4)	−0.0590 (2)	0.103 (2)
H9A	−0.3666	0.7843	−0.0608	0.154*
H9B	−0.3361	0.8914	−0.0925	0.154*
H9C	−0.4515	0.8834	−0.0597	0.154*
C10	0.3443 (3)	0.8186 (2)	0.15288 (14)	0.0348 (8)
C11	0.4389 (3)	0.7569 (3)	0.14243 (15)	0.0397 (8)
H11A	0.5140	0.7590	0.1625	0.048*
C12	0.4010 (3)	0.6923 (2)	0.09694 (15)	0.0376 (8)
C13	0.4651 (3)	0.6068 (3)	0.06842 (18)	0.0603 (11)
H13A	0.4620	0.6201	0.0265	0.090*
H13B	0.4292	0.5387	0.0753	0.090*
H13C	0.5460	0.6059	0.0849	0.090*
C14	0.3437 (3)	0.8999 (3)	0.19951 (15)	0.0406 (8)
C15	0.2368 (3)	1.0570 (3)	0.23400 (16)	0.0556 (11)
C16	0.2145 (4)	1.0084 (4)	0.29185 (17)	0.0814 (15)
H16A	0.1502	0.9584	0.2861	0.122*
H16B	0.1946	1.0639	0.3187	0.122*
H16C	0.2842	0.9716	0.3082	0.122*
C17	0.1295 (4)	1.1166 (4)	0.20908 (19)	0.0776 (15)
H17A	0.0646	1.0675	0.2023	0.116*
H17B	0.1450	1.1498	0.1722	0.116*
H17C	0.1100	1.1710	0.2367	0.116*
C18	0.3393 (4)	1.1333 (3)	0.24134 (19)	0.0761 (14)
H18A	0.4103	1.0940	0.2531	0.114*
H18B	0.3258	1.1854	0.2713	0.114*
H18C	0.3474	1.1692	0.2044	0.114*
C19	−0.0178 (3)	0.5527 (3)	0.12226 (15)	0.0422 (9)
C20	0.0198 (3)	0.4572 (3)	0.10058 (15)	0.0424 (9)
H20A	−0.0073	0.3887	0.1087	0.051*
C21	0.1040 (3)	0.4833 (2)	0.06523 (14)	0.0379 (8)
C22	0.1724 (4)	0.4122 (3)	0.03011 (18)	0.0609 (12)
H22A	0.2552	0.4238	0.0406	0.091*
H22B	0.1540	0.4273	−0.0113	0.091*
H22C	0.1530	0.3388	0.0380	0.091*
C23	−0.1086 (3)	0.5782 (3)	0.16117 (16)	0.0496 (10)
C24	−0.2191 (3)	0.5001 (3)	0.24013 (18)	0.0606 (11)
C25	−0.1815 (6)	0.5755 (4)	0.2880 (2)	0.133 (3)
H25A	−0.1747	0.6463	0.2718	0.200*
H25B	−0.1063	0.5534	0.3069	0.200*
H25C	−0.2389	0.5761	0.3167	0.200*
C26	−0.3366 (4)	0.5287 (5)	0.2105 (3)	0.133 (3)
H26A	−0.3371	0.6032	0.1994	0.199*
H26B	−0.3962	0.5161	0.2372	0.199*
H26C	−0.3527	0.4853	0.1756	0.199*
C27	−0.2234 (4)	0.3897 (4)	0.2646 (2)	0.0893 (17)
H27A	−0.1463	0.3695	0.2819	0.134*
H27B	−0.2485	0.3404	0.2333	0.134*
H27C	−0.2783	0.3876	0.2945	0.134*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Tl1	0.04755 (9)	0.04034 (8)	0.04461 (9)	0.00383 (7)	0.01116 (6)	−0.00392 (7)
B1	0.038 (2)	0.029 (2)	0.0287 (19)	0.0028 (17)	0.0019 (16)	−0.0004 (16)
O1	0.0483 (15)	0.0426 (15)	0.0460 (15)	0.0054 (12)	−0.0013 (12)	0.0165 (12)
O2	0.0524 (17)	0.0584 (17)	0.0474 (16)	0.0094 (13)	−0.0168 (14)	−0.0117 (13)
O3	0.097 (3)	0.0558 (19)	0.120 (3)	0.0328 (18)	0.053 (2)	0.0380 (19)
N1	0.0359 (17)	0.0331 (15)	0.0316 (15)	0.0036 (12)	0.0050 (13)	0.0010 (12)
N2	0.0335 (16)	0.0306 (15)	0.0293 (15)	0.0013 (12)	0.0011 (12)	0.0000 (12)
N3	0.0419 (19)	0.0379 (18)	0.049 (2)	0.0051 (14)	0.0036 (16)	0.0081 (14)
N4	0.0366 (17)	0.0294 (14)	0.0334 (15)	0.0032 (12)	0.0008 (13)	−0.0005 (12)
N5	0.0359 (17)	0.0293 (14)	0.0327 (15)	0.0029 (12)	0.0006 (13)	−0.0003 (12)
N6	0.051 (2)	0.0494 (19)	0.0327 (17)	0.0065 (16)	−0.0096 (15)	−0.0123 (15)
N7	0.0444 (18)	0.0320 (15)	0.0391 (17)	0.0014 (13)	0.0058 (14)	0.0012 (13)
N8	0.0410 (17)	0.0280 (15)	0.0336 (16)	0.0004 (12)	−0.0003 (13)	−0.0020 (12)
N9	0.044 (2)	0.047 (2)	0.0521 (19)	0.0019 (15)	0.0102 (16)	0.0143 (16)
C1	0.0345 (19)	0.0287 (18)	0.0339 (18)	−0.0029 (14)	0.0009 (15)	0.0016 (14)
C2	0.038 (2)	0.052 (2)	0.0314 (18)	−0.0024 (17)	0.0011 (15)	0.0113 (17)
C3	0.037 (2)	0.044 (2)	0.0339 (19)	−0.0012 (16)	0.0023 (16)	−0.0004 (16)
C4	0.057 (3)	0.076 (3)	0.049 (2)	0.016 (2)	0.022 (2)	0.018 (2)
C5	0.036 (2)	0.0348 (19)	0.038 (2)	−0.0046 (15)	0.0025 (16)	0.0011 (16)
C6	0.036 (2)	0.046 (2)	0.066 (3)	0.0046 (17)	0.010 (2)	0.001 (2)
C7	0.068 (4)	0.154 (6)	0.131 (5)	0.026 (3)	0.052 (3)	0.073 (4)
C8	0.055 (3)	0.058 (3)	0.158 (5)	0.009 (2)	0.028 (3)	−0.019 (3)
C9	0.045 (3)	0.127 (5)	0.134 (5)	−0.005 (3)	−0.006 (3)	−0.056 (4)
C10	0.0354 (19)	0.0338 (19)	0.0345 (18)	−0.0036 (15)	−0.0013 (15)	0.0038 (15)
C11	0.033 (2)	0.040 (2)	0.044 (2)	0.0020 (16)	−0.0037 (16)	−0.0015 (17)
C12	0.036 (2)	0.037 (2)	0.040 (2)	0.0024 (15)	0.0041 (16)	0.0027 (15)
C13	0.043 (2)	0.059 (3)	0.077 (3)	0.014 (2)	−0.003 (2)	−0.016 (2)
C14	0.043 (2)	0.038 (2)	0.040 (2)	−0.0009 (17)	−0.0005 (18)	−0.0027 (17)
C15	0.053 (3)	0.066 (3)	0.045 (2)	0.014 (2)	−0.012 (2)	−0.025 (2)
C16	0.082 (4)	0.115 (4)	0.047 (3)	0.022 (3)	0.009 (2)	−0.010 (3)
C17	0.074 (3)	0.084 (3)	0.069 (3)	0.034 (3)	−0.019 (3)	−0.032 (3)
C18	0.084 (4)	0.064 (3)	0.076 (3)	0.004 (3)	−0.014 (3)	−0.031 (2)
C19	0.044 (2)	0.039 (2)	0.041 (2)	−0.0045 (16)	−0.0036 (18)	0.0077 (17)
C20	0.050 (2)	0.0240 (18)	0.052 (2)	−0.0049 (16)	−0.0051 (19)	−0.0002 (16)
C21	0.046 (2)	0.0257 (17)	0.041 (2)	−0.0035 (15)	−0.0035 (17)	−0.0018 (15)
C22	0.074 (3)	0.034 (2)	0.076 (3)	−0.001 (2)	0.013 (2)	−0.014 (2)
C23	0.050 (2)	0.050 (2)	0.050 (2)	−0.0042 (19)	0.006 (2)	0.0107 (19)
C24	0.054 (3)	0.069 (3)	0.062 (3)	0.002 (2)	0.022 (2)	0.016 (2)
C25	0.191 (7)	0.112 (5)	0.109 (5)	−0.050 (5)	0.078 (5)	−0.039 (4)
C26	0.054 (3)	0.199 (7)	0.151 (6)	0.038 (4)	0.042 (4)	0.093 (5)
C27	0.086 (4)	0.083 (3)	0.106 (4)	−0.006 (3)	0.047 (3)	0.043 (3)

Geometric parameters (Å, º)

Tl1—N1	2.739 (3)	C8—H8C	0.9800
Tl1—N4	2.747 (3)	C9—H9A	0.9800
Tl1—N7	2.566 (3)	C9—H9B	0.9800
B1—N8	1.539 (4)	C9—H9C	0.9800
B1—N5	1.552 (4)	C10—C11	1.388 (4)
B1—N2	1.548 (4)	C10—C14	1.492 (4)
B1—H1B	1.12 (3)	C11—C12	1.374 (4)
O1—C5	1.228 (4)	C11—H11A	0.9500
O2—C14	1.227 (4)	C12—C13	1.501 (5)
O3—C23	1.219 (4)	C13—H13A	0.9800
N1—C1	1.343 (4)	C13—H13B	0.9800
N1—N2	1.357 (3)	C13—H13C	0.9800
N2—C3	1.364 (4)	C15—C16	1.515 (5)
N3—C5	1.339 (4)	C15—C17	1.525 (5)
N3—C6	1.482 (4)	C15—C18	1.531 (5)
N3—H3N	0.77 (3)	C16—H16A	0.9800
N4—C10	1.338 (4)	C16—H16B	0.9800
N4—N5	1.366 (3)	C16—H16C	0.9800
N5—C12	1.361 (4)	C17—H17A	0.9800
N6—C14	1.347 (4)	C17—H17B	0.9800
N6—C15	1.480 (4)	C17—H17C	0.9800
N6—H6N	0.73 (3)	C18—H18A	0.9800
N7—C19	1.339 (4)	C18—H18B	0.9800
N7—N8	1.355 (4)	C18—H18C	0.9800
N8—C21	1.362 (4)	C19—C20	1.397 (5)
N9—C23	1.350 (4)	C19—C23	1.481 (5)
N9—C24	1.465 (5)	C20—C21	1.369 (5)
N9—H9N	0.79 (3)	C20—H20A	0.9500
C1—C2	1.390 (4)	C21—C22	1.489 (5)
C1—C5	1.481 (4)	C22—H22A	0.9800
C2—C3	1.373 (4)	C22—H22B	0.9800
C2—H2A	0.9500	C22—H22C	0.9800
C3—C4	1.490 (5)	C24—C25	1.498 (6)
C4—H4A	0.9800	C24—C26	1.515 (6)
C4—H4B	0.9800	C24—C27	1.515 (6)
C4—H4C	0.9800	C25—H25A	0.9800
C6—C7	1.489 (6)	C25—H25B	0.9800
C6—C8	1.507 (5)	C25—H25C	0.9800
C6—C9	1.524 (6)	C26—H26A	0.9800
C7—H7A	0.9800	C26—H26B	0.9800
C7—H7B	0.9800	C26—H26C	0.9800
C7—H7C	0.9800	C27—H27A	0.9800
C8—H8A	0.9800	C27—H27B	0.9800
C8—H8B	0.9800	C27—H27C	0.9800
N7—Tl1—N1	66.71 (8)	C12—C11—C10	105.5 (3)
N7—Tl1—N4	73.15 (8)	C12—C11—H11A	127.2
N1—Tl1—N4	75.05 (8)	C10—C11—H11A	127.2
N8—B1—N5	110.4 (3)	N5—C12—C11	107.2 (3)
N8—B1—N2	110.3 (3)	N5—C12—C13	123.6 (3)
N5—B1—N2	110.6 (3)	C11—C12—C13	129.1 (3)
N8—B1—H1B	108.5 (15)	C12—C13—H13A	109.5
N5—B1—H1B	107.2 (15)	C12—C13—H13B	109.5
N2—B1—H1B	109.8 (15)	H13A—C13—H13B	109.5
C1—N1—N2	105.7 (3)	C12—C13—H13C	109.5
C1—N1—Tl1	128.5 (2)	H13A—C13—H13C	109.5
N2—N1—Tl1	116.75 (18)	H13B—C13—H13C	109.5
N1—N2—C3	110.5 (3)	O2—C14—N6	124.4 (3)
N1—N2—B1	123.0 (3)	O2—C14—C10	119.7 (3)
C3—N2—B1	126.4 (3)	N6—C14—C10	115.9 (3)
C5—N3—C6	128.5 (3)	N6—C15—C16	109.6 (3)
C5—N3—H3N	116 (3)	N6—C15—C17	107.4 (3)
C6—N3—H3N	115 (3)	C16—C15—C17	109.6 (4)
C10—N4—N5	105.3 (3)	N6—C15—C18	110.3 (3)
C10—N4—Tl1	131.5 (2)	C16—C15—C18	110.7 (3)
N5—N4—Tl1	120.47 (19)	C17—C15—C18	109.1 (4)
C12—N5—N4	110.7 (3)	C15—C16—H16A	109.5
C12—N5—B1	127.2 (3)	C15—C16—H16B	109.5
N4—N5—B1	122.0 (3)	H16A—C16—H16B	109.5
C14—N6—C15	125.8 (3)	C15—C16—H16C	109.5
C14—N6—H6N	121 (3)	H16A—C16—H16C	109.5
C15—N6—H6N	113 (3)	H16B—C16—H16C	109.5
C19—N7—N8	106.8 (3)	C15—C17—H17A	109.5
C19—N7—Tl1	126.9 (2)	C15—C17—H17B	109.5
N8—N7—Tl1	126.2 (2)	H17A—C17—H17B	109.5
N7—N8—C21	109.7 (3)	C15—C17—H17C	109.5
N7—N8—B1	121.5 (3)	H17A—C17—H17C	109.5
C21—N8—B1	128.8 (3)	H17B—C17—H17C	109.5
C23—N9—C24	127.5 (3)	C15—C18—H18A	109.5
C23—N9—H9N	113 (3)	C15—C18—H18B	109.5
C24—N9—H9N	115 (3)	H18A—C18—H18B	109.5
N1—C1—C2	110.9 (3)	C15—C18—H18C	109.5
N1—C1—C5	121.1 (3)	H18A—C18—H18C	109.5
C2—C1—C5	127.7 (3)	H18B—C18—H18C	109.5
C3—C2—C1	105.5 (3)	N7—C19—C20	110.0 (3)
C3—C2—H2A	127.3	N7—C19—C23	117.9 (3)
C1—C2—H2A	127.3	C20—C19—C23	132.0 (3)
N2—C3—C2	107.4 (3)	C21—C20—C19	105.5 (3)
N2—C3—C4	122.8 (3)	C21—C20—H20A	127.3
C2—C3—C4	129.8 (3)	C19—C20—H20A	127.3
C3—C4—H4A	109.5	N8—C21—C20	108.0 (3)
C3—C4—H4B	109.5	N8—C21—C22	123.5 (3)
H4A—C4—H4B	109.5	C20—C21—C22	128.5 (3)
C3—C4—H4C	109.5	C21—C22—H22A	109.5
H4A—C4—H4C	109.5	C21—C22—H22B	109.5
H4B—C4—H4C	109.5	H22A—C22—H22B	109.5
O1—C5—N3	123.9 (3)	C21—C22—H22C	109.5
O1—C5—C1	121.6 (3)	H22A—C22—H22C	109.5
N3—C5—C1	114.4 (3)	H22B—C22—H22C	109.5
N3—C6—C7	106.9 (3)	O3—C23—N9	124.2 (4)
N3—C6—C8	110.5 (3)	O3—C23—C19	121.2 (3)
C7—C6—C8	112.2 (4)	N9—C23—C19	114.5 (3)
N3—C6—C9	108.1 (3)	N9—C24—C25	109.7 (4)
C7—C6—C9	109.6 (4)	N9—C24—C26	109.3 (4)
C8—C6—C9	109.5 (4)	C25—C24—C26	111.7 (5)
C6—C7—H7A	109.5	N9—C24—C27	107.1 (3)
C6—C7—H7B	109.5	C25—C24—C27	109.5 (4)
H7A—C7—H7B	109.5	C26—C24—C27	109.4 (4)
C6—C7—H7C	109.5	C24—C25—H25A	109.5
H7A—C7—H7C	109.5	C24—C25—H25B	109.5
H7B—C7—H7C	109.5	H25A—C25—H25B	109.5
C6—C8—H8A	109.5	C24—C25—H25C	109.5
C6—C8—H8B	109.5	H25A—C25—H25C	109.5
H8A—C8—H8B	109.5	H25B—C25—H25C	109.5
C6—C8—H8C	109.5	C24—C26—H26A	109.5
H8A—C8—H8C	109.5	C24—C26—H26B	109.5
H8B—C8—H8C	109.5	H26A—C26—H26B	109.5
C6—C9—H9A	109.5	C24—C26—H26C	109.5
C6—C9—H9B	109.5	H26A—C26—H26C	109.5
H9A—C9—H9B	109.5	H26B—C26—H26C	109.5
C6—C9—H9C	109.5	C24—C27—H27A	109.5
H9A—C9—H9C	109.5	C24—C27—H27B	109.5
H9B—C9—H9C	109.5	H27A—C27—H27B	109.5
N4—C10—C11	111.3 (3)	C24—C27—H27C	109.5
N4—C10—C14	123.8 (3)	H27A—C27—H27C	109.5
C11—C10—C14	124.9 (3)	H27B—C27—H27C	109.5
N7—Tl1—N1—C1	158.4 (3)	N1—C1—C5—O1	165.4 (3)
N4—Tl1—N1—C1	−123.8 (3)	C2—C1—C5—O1	−21.8 (5)
N7—Tl1—N1—N2	−59.5 (2)	N1—C1—C5—N3	−17.3 (4)
N4—Tl1—N1—N2	18.23 (19)	C2—C1—C5—N3	155.6 (3)
C1—N1—N2—C3	−0.1 (3)	C5—N3—C6—C7	−177.1 (4)
Tl1—N1—N2—C3	−150.1 (2)	C5—N3—C6—C8	−54.8 (5)
C1—N1—N2—B1	−177.4 (3)	C5—N3—C6—C9	65.0 (5)
Tl1—N1—N2—B1	32.6 (3)	N5—N4—C10—C11	−0.4 (4)
N8—B1—N2—N1	37.4 (4)	Tl1—N4—C10—C11	160.1 (2)
N5—B1—N2—N1	−85.0 (4)	N5—N4—C10—C14	−178.3 (3)
N8—B1—N2—C3	−139.5 (3)	Tl1—N4—C10—C14	−17.8 (5)
N5—B1—N2—C3	98.1 (4)	N4—C10—C11—C12	0.9 (4)
N7—Tl1—N4—C10	−129.3 (3)	C14—C10—C11—C12	178.8 (3)
N1—Tl1—N4—C10	161.0 (3)	N4—N5—C12—C11	0.9 (4)
N7—Tl1—N4—N5	28.8 (2)	B1—N5—C12—C11	−175.6 (3)
N1—Tl1—N4—N5	−40.9 (2)	N4—N5—C12—C13	177.9 (3)
C10—N4—N5—C12	−0.3 (3)	B1—N5—C12—C13	1.4 (5)
Tl1—N4—N5—C12	−163.4 (2)	C10—C11—C12—N5	−1.1 (4)
C10—N4—N5—B1	176.4 (3)	C10—C11—C12—C13	−177.9 (4)
Tl1—N4—N5—B1	13.3 (3)	C15—N6—C14—O2	−3.1 (6)
N8—B1—N5—C12	106.7 (4)	C15—N6—C14—C10	176.0 (3)
N2—B1—N5—C12	−131.0 (3)	N4—C10—C14—O2	156.8 (3)
N8—B1—N5—N4	−69.4 (4)	C11—C10—C14—O2	−20.8 (5)
N2—B1—N5—N4	52.9 (4)	N4—C10—C14—N6	−22.3 (5)
N1—Tl1—N7—C19	−135.8 (3)	C11—C10—C14—N6	160.1 (3)
N4—Tl1—N7—C19	143.6 (3)	C14—N6—C15—C16	−57.7 (5)
N1—Tl1—N7—N8	43.1 (2)	C14—N6—C15—C17	−176.8 (4)
N4—Tl1—N7—N8	−37.6 (2)	C14—N6—C15—C18	64.4 (5)
C19—N7—N8—C21	−0.6 (4)	N8—N7—C19—C20	1.1 (4)
Tl1—N7—N8—C21	−179.6 (2)	Tl1—N7—C19—C20	−179.8 (2)
C19—N7—N8—B1	−178.3 (3)	N8—N7—C19—C23	−178.3 (3)
Tl1—N7—N8—B1	2.7 (4)	Tl1—N7—C19—C23	0.7 (4)
N5—B1—N8—N7	61.3 (4)	N7—C19—C20—C21	−1.3 (4)
N2—B1—N8—N7	−61.2 (4)	C23—C19—C20—C21	178.1 (4)
N5—B1—N8—C21	−115.9 (3)	N7—N8—C21—C20	−0.2 (4)
N2—B1—N8—C21	121.6 (3)	B1—N8—C21—C20	177.3 (3)
N2—N1—C1—C2	−0.2 (3)	N7—N8—C21—C22	179.6 (3)
Tl1—N1—C1—C2	145.0 (2)	B1—N8—C21—C22	−2.9 (5)
N2—N1—C1—C5	173.7 (3)	C19—C20—C21—N8	0.9 (4)
Tl1—N1—C1—C5	−41.0 (4)	C19—C20—C21—C22	−178.9 (3)
N1—C1—C2—C3	0.4 (4)	C24—N9—C23—O3	−2.2 (7)
C5—C1—C2—C3	−173.1 (3)	C24—N9—C23—C19	−180.0 (3)
N1—N2—C3—C2	0.3 (4)	N7—C19—C23—O3	26.6 (6)
B1—N2—C3—C2	177.5 (3)	C20—C19—C23—O3	−152.8 (4)
N1—N2—C3—C4	−179.6 (3)	N7—C19—C23—N9	−155.6 (3)
B1—N2—C3—C4	−2.4 (5)	C20—C19—C23—N9	25.1 (6)
C1—C2—C3—N2	−0.4 (4)	C23—N9—C24—C25	−66.8 (5)
C1—C2—C3—C4	179.4 (4)	C23—N9—C24—C26	56.0 (6)
C6—N3—C5—O1	6.5 (6)	C23—N9—C24—C27	174.4 (4)
C6—N3—C5—C1	−170.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6N···O1^i	0.73 (3)	2.28 (3)	3.011 (4)	174 (4)
N9—H9N···O2^ii	0.79 (3)	2.36 (4)	3.073 (4)	151 (4)

Symmetry codes: (i) −x, −y+2, −z; (ii) −x+1/2, y−1/2, −z+1/2.

(IV) Carbonyl[tris(3-anilinocarbonyl-5-methylpyrazol-1-yl-κN²)borato]copper(I) tetrahydrofuran trisolvate

Crystal data

[Cu(C33H31BN9O3)(CO)]·3C4H8O	Z = 4
Mr = 920.34	F(000) = 1936
Triclinic, P1	Dx = 1.309 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 13.1310 (15) Å	Cell parameters from 5795 reflections
b = 19.404 (2) Å	θ = 2.2–20.2°
c = 19.771 (2) Å	µ = 0.53 mm^−1
α = 97.840 (2)°	T = 200 K
β = 107.809 (2)°	Block, colourless
γ = 97.599 (2)°	0.29 × 0.29 × 0.16 mm
V = 4669.6 (9) Å^3

Data collection

Bruker APEXII area-detector diffractometer	21442 independent reflections
Radiation source: fine-focus sealed tube	12780 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
Detector resolution: 8.33 pixels mm^-1	θmax = 27.6°, θmin = 1.7°
ϕ and ω scans	h = −17→17
Absorption correction: multi-scan (APEX2; Bruker, 2007)	k = −25→25
Tmin = 0.863, Tmax = 0.920	l = −25→25
62383 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.058P)^2 + 0.6272P] where P = (Fo^2 + 2Fc^2)/3
21442 reflections	(Δ/σ)max = 0.001
1177 parameters	Δρmax = 0.60 e Å^−3
95 restraints	Δρmin = −0.49 e Å^−3

Special details

Experimental. Data collection is performed with four batch runs at ϕ = 0.00° (600 frames), at ϕ = 90.00° (600 frames), at ϕ = 180° (600 frames) and at ϕ = 270° (600 frames). Frame width = 0.30° in ω.

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.

Data crystals were selected, sectioned if necessary, mounted on plastic mesh with viscous oil and cooled to 200 K. Diffraction data were collected on a Bruker APEXII DUO diffractometer, using Mo Kα radiation monochromated by graphite.

Data were corrected for absorption using multi-scan methods (Bruker, 2007), and the structure was solved using direct methods and refined using full-matrix least-squares based on F² with atomic scattering factors contained in the SHELX program suite (Sheldrick, 2008).

No symmetry higher than triclinic was observed for (IV) and refinement in the centrosymmetric space group P1 yielded chemically reasonable and computationally stable results of refinement.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.52095 (3)	0.118786 (18)	0.763430 (19)	0.03229 (10)
Cu2	0.97063 (3)	0.598461 (18)	0.735913 (19)	0.03190 (10)
B1	0.6368 (3)	0.26064 (18)	0.74871 (18)	0.0344 (8)
H1	0.6745	0.3071	0.7439	0.041*
B2	1.0794 (2)	0.73173 (17)	0.69923 (18)	0.0300 (7)
H2	1.1152	0.7751	0.6873	0.036*
N1	0.60295 (18)	0.13246 (12)	0.69006 (12)	0.0323 (5)
N2	0.64339 (18)	0.20111 (12)	0.69064 (12)	0.0332 (6)
N3	0.6112 (2)	−0.02160 (14)	0.56727 (14)	0.0404 (6)
H3A	0.638 (2)	0.0010 (15)	0.5429 (16)	0.048*
N4	0.44858 (18)	0.20501 (12)	0.74191 (12)	0.0313 (5)
N5	0.51617 (19)	0.26367 (12)	0.73938 (12)	0.0336 (6)
N6	0.1794 (2)	0.19426 (13)	0.75120 (14)	0.0353 (6)
H6A	0.198 (2)	0.2352 (10)	0.7720 (15)	0.042*
N7	0.65173 (18)	0.18429 (12)	0.84354 (12)	0.0320 (5)
N8	0.69416 (18)	0.24364 (12)	0.82429 (12)	0.0319 (5)
N9	0.77540 (19)	0.10591 (13)	0.99461 (13)	0.0349 (6)
H9A	0.8370 (16)	0.1262 (15)	1.0008 (16)	0.042*
N10	0.89593 (17)	0.68143 (12)	0.70367 (12)	0.0303 (5)
N11	0.95894 (17)	0.73560 (11)	0.68950 (12)	0.0296 (5)
N12	0.63353 (19)	0.68905 (13)	0.71966 (14)	0.0352 (6)
H12A	0.645 (2)	0.7321 (10)	0.7257 (16)	0.042*
N13	1.10448 (18)	0.66978 (12)	0.80558 (12)	0.0314 (5)
N14	1.13865 (17)	0.72632 (12)	0.77878 (12)	0.0300 (5)
N15	1.2459 (2)	0.60561 (14)	0.96012 (14)	0.0388 (6)
H15A	1.3072 (17)	0.6243 (15)	0.9619 (17)	0.047*
N16	1.04614 (17)	0.59943 (12)	0.65786 (12)	0.0307 (5)
N17	1.08394 (17)	0.66490 (12)	0.64809 (12)	0.0281 (5)
N18	1.0996 (2)	0.43489 (13)	0.58172 (14)	0.0365 (6)
H18A	1.142 (2)	0.4560 (15)	0.5659 (16)	0.044*
O1	0.5595 (2)	−0.01420 (11)	0.66730 (12)	0.0527 (6)
O2	0.25051 (18)	0.10611 (11)	0.70423 (13)	0.0543 (6)
O3	0.59571 (17)	0.09371 (12)	0.93023 (12)	0.0535 (6)
O4	0.4179 (2)	−0.01976 (12)	0.77656 (13)	0.0595 (7)
O5	0.70666 (17)	0.59026 (11)	0.70438 (13)	0.0484 (6)
O6	1.06235 (18)	0.59313 (14)	0.90895 (13)	0.0657 (8)
O7	0.96940 (18)	0.45221 (11)	0.63337 (13)	0.0519 (6)
O8	0.8579 (2)	0.47057 (14)	0.76398 (16)	0.0768 (8)
C1	0.6239 (2)	0.09311 (15)	0.63645 (15)	0.0334 (7)
C2	0.6776 (2)	0.13654 (17)	0.60223 (16)	0.0396 (7)
H2A	0.7009	0.1220	0.5624	0.048*
C3	0.6895 (2)	0.20432 (17)	0.63778 (16)	0.0385 (7)
C4	0.5945 (2)	0.01464 (16)	0.62587 (16)	0.0359 (7)
C5	0.5487 (3)	−0.14483 (17)	0.57794 (17)	0.0432 (8)
H5	0.5324	−0.1292	0.6205	0.052*
C6	0.5312 (3)	−0.21661 (18)	0.54959 (18)	0.0516 (9)
H6	0.5028	−0.2500	0.5732	0.062*
C7	0.5541 (3)	−0.24044 (19)	0.48773 (19)	0.0557 (9)
H7	0.5417	−0.2897	0.4689	0.067*
C8	0.5954 (3)	−0.19174 (19)	0.45367 (18)	0.0519 (9)
H8	0.6112	−0.2075	0.4110	0.062*
C9	0.6138 (3)	−0.12025 (18)	0.48114 (17)	0.0466 (8)
H9	0.6426	−0.0872	0.4574	0.056*
C10	0.5905 (2)	−0.09608 (17)	0.54330 (16)	0.0382 (7)
C11	0.7421 (3)	0.27270 (18)	0.62552 (19)	0.0541 (9)
H11A	0.6894	0.3045	0.6165	0.081*
H11B	0.7666	0.2635	0.5836	0.081*
H11C	0.8047	0.2948	0.6684	0.081*
C12	0.3507 (2)	0.22308 (15)	0.73146 (15)	0.0324 (6)
C13	0.3542 (3)	0.29270 (16)	0.72136 (16)	0.0405 (7)
H13	0.2958	0.3181	0.7128	0.049*
C14	0.4604 (3)	0.31714 (15)	0.72637 (16)	0.0378 (7)
C15	0.2559 (2)	0.16857 (16)	0.72721 (15)	0.0344 (7)
C16	0.0309 (3)	0.09069 (17)	0.70708 (17)	0.0456 (8)
H16	0.0667	0.0679	0.6778	0.055*
C17	−0.0697 (3)	0.05754 (19)	0.70701 (19)	0.0528 (9)
H17	−0.1020	0.0123	0.6774	0.063*
C18	−0.1234 (3)	0.08869 (18)	0.74877 (18)	0.0480 (8)
H18	−0.1917	0.0654	0.7488	0.058*
C19	−0.0763 (3)	0.1540 (2)	0.7903 (2)	0.0640 (11)
H19	−0.1129	0.1767	0.8191	0.077*
C20	0.0234 (3)	0.18763 (18)	0.7912 (2)	0.0583 (10)
H20	0.0550	0.2329	0.8208	0.070*
C21	0.0783 (2)	0.15588 (15)	0.74906 (15)	0.0338 (7)
C22	0.5117 (3)	0.38783 (16)	0.7172 (2)	0.0583 (10)
H22A	0.5650	0.4128	0.7635	0.088*
H22B	0.4552	0.4160	0.7011	0.088*
H22C	0.5482	0.3807	0.6811	0.088*
C23	0.7195 (2)	0.18122 (14)	0.90871 (15)	0.0309 (6)
C24	0.8068 (2)	0.23872 (15)	0.93214 (16)	0.0343 (7)
H24	0.8660	0.2490	0.9763	0.041*
C25	0.7879 (2)	0.27715 (15)	0.87715 (16)	0.0340 (7)
C26	0.6903 (2)	0.12270 (15)	0.94513 (15)	0.0343 (7)
C27	0.6757 (3)	0.01965 (15)	1.04380 (15)	0.0371 (7)
H27	0.6078	0.0289	1.0157	0.045*
C28	0.6788 (3)	−0.02871 (17)	1.08951 (17)	0.0467 (8)
H28	0.6127	−0.0527	1.0922	0.056*
C29	0.7756 (3)	−0.0424 (2)	1.1307 (2)	0.0713 (12)
H29	0.7769	−0.0751	1.1625	0.086*
C30	0.8719 (3)	−0.0082 (2)	1.1258 (2)	0.0820 (14)
H30	0.9396	−0.0177	1.1539	0.098*
C31	0.8695 (3)	0.03998 (19)	1.0796 (2)	0.0585 (10)
H31	0.9356	0.0630	1.0760	0.070*
C32	0.7719 (2)	0.05463 (15)	1.03912 (15)	0.0352 (7)
C33	0.8563 (3)	0.34241 (16)	0.87051 (18)	0.0501 (9)
H33A	0.8868	0.3308	0.8318	0.075*
H33B	0.9156	0.3607	0.9163	0.075*
H33C	0.8113	0.3784	0.8590	0.075*
C34	0.4565 (2)	0.03455 (16)	0.77206 (16)	0.0376 (7)
C35	0.7983 (2)	0.70055 (14)	0.69290 (15)	0.0299 (6)
C36	0.7987 (2)	0.76610 (16)	0.67187 (16)	0.0375 (7)
H36	0.7399	0.7911	0.6610	0.045*
C37	0.9021 (2)	0.78731 (15)	0.67010 (16)	0.0345 (7)
C38	0.7098 (2)	0.65347 (16)	0.70632 (15)	0.0338 (7)
C39	0.5185 (2)	0.59466 (18)	0.74910 (17)	0.0428 (8)
H39	0.5722	0.5656	0.7544	0.051*
C40	0.4204 (3)	0.57171 (19)	0.75968 (18)	0.0489 (9)
H40	0.4077	0.5266	0.7723	0.059*
C41	0.3414 (3)	0.61288 (19)	0.75225 (17)	0.0490 (9)
H41	0.2750	0.5965	0.7597	0.059*
C42	0.3598 (2)	0.67784 (18)	0.73392 (17)	0.0436 (8)
H42	0.3058	0.7066	0.7288	0.052*
C43	0.4563 (2)	0.70193 (17)	0.72285 (16)	0.0390 (7)
H43	0.4680	0.7469	0.7098	0.047*
C44	0.5365 (2)	0.66029 (16)	0.73078 (15)	0.0322 (7)
C45	0.9494 (3)	0.85372 (17)	0.6515 (2)	0.0507 (9)
H45A	1.0047	0.8828	0.6949	0.076*
H45B	0.8916	0.8803	0.6329	0.076*
H45C	0.9829	0.8416	0.6145	0.076*
C46	1.1734 (2)	0.67667 (16)	0.87306 (15)	0.0342 (7)
C47	1.2512 (2)	0.73860 (16)	0.89045 (16)	0.0363 (7)
H47	1.3089	0.7559	0.9348	0.044*
C48	1.2269 (2)	0.76941 (15)	0.82967 (16)	0.0326 (7)
C49	1.1544 (2)	0.62151 (17)	0.91571 (16)	0.0385 (7)
C50	1.1637 (3)	0.51337 (17)	1.01253 (18)	0.0491 (8)
H50	1.0923	0.5195	0.9872	0.059*
C51	1.1784 (3)	0.46415 (19)	1.0576 (2)	0.0590 (10)
H51	1.1168	0.4375	1.0636	0.071*
C52	1.2799 (3)	0.4532 (2)	1.0935 (2)	0.0721 (12)
H52	1.2887	0.4193	1.1243	0.087*
C53	1.3699 (3)	0.4917 (2)	1.0848 (2)	0.0799 (14)
H53	1.4408	0.4842	1.1094	0.096*
C54	1.3561 (3)	0.54163 (19)	1.03989 (19)	0.0594 (10)
H54	1.4181	0.5676	1.0336	0.071*
C55	1.2534 (3)	0.55382 (16)	1.00434 (16)	0.0404 (7)
C56	1.2827 (3)	0.83633 (16)	0.81723 (17)	0.0439 (8)
H56A	1.3035	0.8263	0.7739	0.066*
H56B	1.3479	0.8563	0.8591	0.066*
H56C	1.2331	0.8703	0.8105	0.066*
C57	1.0682 (2)	0.55288 (15)	0.60995 (15)	0.0314 (6)
C58	1.1190 (2)	0.58826 (15)	0.56909 (15)	0.0351 (7)
H58	1.1426	0.5676	0.5315	0.042*
C59	1.1281 (2)	0.65918 (16)	0.59393 (15)	0.0330 (7)
C60	1.0396 (2)	0.47546 (16)	0.60942 (16)	0.0359 (7)
C61	1.0310 (3)	0.31850 (17)	0.60482 (18)	0.0469 (8)
H61	0.9888	0.3388	0.6308	0.056*
C62	1.0321 (3)	0.24596 (18)	0.59660 (19)	0.0567 (10)
H62	0.9898	0.2171	0.6171	0.068*
C63	1.0929 (3)	0.21551 (19)	0.5596 (2)	0.0584 (10)
H63	1.0940	0.1663	0.5552	0.070*
C64	1.1524 (3)	0.25750 (19)	0.5289 (2)	0.0598 (10)
H64	1.1939	0.2369	0.5026	0.072*
C65	1.1521 (3)	0.32926 (18)	0.53611 (18)	0.0502 (9)
H65	1.1934	0.3576	0.5146	0.060*
C66	1.0923 (2)	0.36051 (16)	0.57452 (16)	0.0374 (7)
C67	1.1760 (3)	0.72175 (16)	0.57004 (17)	0.0444 (8)
H67A	1.1200	0.7498	0.5525	0.067*
H67B	1.2036	0.7056	0.5310	0.067*
H67C	1.2359	0.7509	0.6109	0.067*
C68	0.9022 (3)	0.51998 (18)	0.75389 (18)	0.0445 (8)
O9	0.7348 (2)	0.03977 (13)	0.47714 (13)	0.0600 (7)
C69	0.8459 (3)	0.0316 (3)	0.5003 (2)	0.0895 (15)
H69A	0.8518	−0.0145	0.5158	0.107*
H69B	0.8892	0.0697	0.5417	0.107*
C70	0.8867 (3)	0.0351 (2)	0.4402 (2)	0.0743 (12)
H70A	0.8939	−0.0126	0.4192	0.089*
H70B	0.9589	0.0665	0.4566	0.089*
C71	0.8061 (3)	0.0639 (2)	0.3859 (2)	0.0586 (10)
H71A	0.8313	0.1149	0.3884	0.070*
H71B	0.7928	0.0381	0.3363	0.070*
C72	0.7071 (3)	0.0525 (3)	0.4067 (2)	0.0981 (17)
H72A	0.6726	0.0949	0.4035	0.118*
H72B	0.6543	0.0116	0.3731	0.118*
O10	0.1914 (2)	0.33982 (13)	0.83641 (16)	0.0757 (8)
C73	0.2803 (4)	0.3863 (2)	0.8865 (3)	0.0845 (14)
H73A	0.3443	0.3629	0.8997	0.101*
H73B	0.2637	0.4028	0.9309	0.101*
C74	0.3018 (4)	0.4461 (2)	0.8512 (3)	0.0827 (14)
H74A	0.3319	0.4907	0.8872	0.099*
H74B	0.3538	0.4376	0.8252	0.099*
C75	0.1952 (4)	0.4494 (2)	0.8005 (3)	0.0937 (15)
H75A	0.1973	0.4458	0.7505	0.112*
H75B	0.1717	0.4942	0.8142	0.112*
C76	0.1205 (4)	0.3869 (3)	0.8069 (3)	0.1009 (17)
H76A	0.0800	0.4015	0.8396	0.121*
H76B	0.0677	0.3638	0.7590	0.121*
O11	1.00949 (19)	0.17461 (13)	1.04236 (13)	0.0588 (6)
C77	1.0793 (3)	0.1885 (2)	1.0009 (2)	0.0803 (11)
H77A	1.0367	0.1818	0.9489	0.096*
H77B	1.1334	0.1569	1.0072	0.096*
C78	1.1336 (4)	0.2637 (3)	1.0302 (3)	0.1099 (14)
H78A	1.2099	0.2706	1.0305	0.132*
H78B	1.0948	0.2953	1.0003	0.132*
C79	1.1301 (4)	0.2790 (3)	1.1034 (3)	0.1019 (14)
H79A	1.1086	0.3255	1.1125	0.122*
H79B	1.2025	0.2802	1.1390	0.122*
C80	1.0501 (3)	0.2226 (2)	1.1094 (2)	0.0693 (10)
H80A	1.0844	0.1980	1.1488	0.083*
H80B	0.9900	0.2424	1.1204	0.083*
O12	0.6789 (2)	0.84528 (12)	0.77710 (14)	0.0644 (7)
C81	0.7562 (4)	0.9067 (2)	0.7827 (2)	0.0788 (11)
H81A	0.7382	0.9246	0.7367	0.095*
H81B	0.8304	0.8957	0.7943	0.095*
C82	0.7495 (5)	0.9608 (2)	0.8426 (3)	0.1090 (14)
H82A	0.8230	0.9801	0.8780	0.131*
H82B	0.7182	1.0004	0.8228	0.131*
C83	0.6815 (4)	0.9261 (2)	0.8767 (3)	0.1045 (14)
H83A	0.6328	0.9570	0.8888	0.125*
H83B	0.7256	0.9123	0.9214	0.125*
C84	0.6183 (4)	0.8629 (2)	0.8214 (2)	0.0909 (12)
H84A	0.6032	0.8229	0.8452	0.109*
H84B	0.5480	0.8732	0.7923	0.109*
O13	1.47122 (17)	0.68059 (12)	0.99508 (12)	0.0500 (6)
C85	1.5337 (3)	0.7123 (2)	0.9555 (2)	0.0665 (11)
H85A	1.4879	0.7100	0.9047	0.080*
H85B	1.5957	0.6883	0.9557	0.080*
C86	1.5734 (3)	0.7886 (2)	0.9952 (2)	0.0747 (12)
H86A	1.6440	0.8085	0.9908	0.090*
H86B	1.5197	0.8187	0.9768	0.090*
C87	1.5849 (4)	0.7822 (2)	1.0716 (2)	0.0742 (12)
H87A	1.6567	0.7709	1.0966	0.089*
H87B	1.5764	0.8266	1.0989	0.089*
C88	1.4962 (3)	0.72375 (19)	1.06424 (19)	0.0599 (10)
H88A	1.5193	0.6958	1.1027	0.072*
H88B	1.4314	0.7426	1.0684	0.072*
O14	1.27113 (19)	0.48568 (12)	0.52043 (12)	0.0547 (6)
C89	1.2708 (3)	0.4734 (2)	0.44789 (18)	0.0591 (10)
H89A	1.1952	0.4595	0.4139	0.071*
H89B	1.3111	0.4350	0.4403	0.071*
C90	1.3241 (4)	0.5402 (2)	0.4360 (2)	0.0853 (14)
H90A	1.2694	0.5675	0.4122	0.102*
H90B	1.3700	0.5310	0.4055	0.102*
C91	1.3926 (4)	0.5797 (2)	0.5105 (3)	0.0954 (16)
H91A	1.4709	0.5864	0.5156	0.115*
H91B	1.3729	0.6267	0.5202	0.115*
C92	1.3684 (3)	0.5342 (2)	0.5609 (2)	0.0726 (12)
H92A	1.4287	0.5086	0.5790	0.087*
H92B	1.3585	0.5634	0.6028	0.087*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0343 (2)	0.0314 (2)	0.0344 (2)	0.00597 (15)	0.01445 (16)	0.00980 (15)
Cu2	0.02769 (19)	0.0323 (2)	0.0398 (2)	0.00594 (15)	0.01562 (16)	0.00941 (16)
B1	0.039 (2)	0.0328 (19)	0.0358 (19)	0.0044 (15)	0.0175 (16)	0.0132 (15)
B2	0.0254 (17)	0.0313 (18)	0.0384 (19)	0.0075 (14)	0.0155 (15)	0.0092 (15)
N1	0.0336 (13)	0.0327 (14)	0.0339 (14)	0.0078 (11)	0.0138 (11)	0.0097 (11)
N2	0.0335 (13)	0.0393 (14)	0.0330 (13)	0.0091 (11)	0.0157 (11)	0.0146 (11)
N3	0.0475 (16)	0.0429 (17)	0.0369 (15)	0.0135 (13)	0.0215 (13)	0.0054 (12)
N4	0.0342 (14)	0.0310 (13)	0.0321 (13)	0.0073 (11)	0.0141 (11)	0.0086 (10)
N5	0.0380 (14)	0.0306 (13)	0.0366 (14)	0.0067 (11)	0.0163 (12)	0.0111 (11)
N6	0.0377 (15)	0.0309 (14)	0.0391 (15)	0.0086 (12)	0.0158 (12)	0.0027 (11)
N7	0.0342 (14)	0.0306 (13)	0.0337 (14)	0.0037 (11)	0.0137 (11)	0.0104 (11)
N8	0.0347 (14)	0.0296 (13)	0.0346 (14)	0.0035 (11)	0.0155 (11)	0.0092 (11)
N9	0.0295 (13)	0.0358 (15)	0.0376 (14)	0.0027 (11)	0.0081 (12)	0.0109 (11)
N10	0.0257 (12)	0.0311 (13)	0.0378 (14)	0.0043 (10)	0.0160 (11)	0.0070 (11)
N11	0.0264 (12)	0.0283 (13)	0.0375 (14)	0.0068 (10)	0.0140 (11)	0.0083 (10)
N12	0.0242 (13)	0.0343 (14)	0.0504 (16)	0.0095 (11)	0.0170 (12)	0.0041 (13)
N13	0.0265 (13)	0.0371 (14)	0.0335 (14)	0.0067 (11)	0.0129 (11)	0.0091 (11)
N14	0.0252 (12)	0.0301 (13)	0.0365 (14)	0.0042 (10)	0.0139 (11)	0.0046 (11)
N15	0.0294 (14)	0.0452 (16)	0.0406 (15)	0.0024 (12)	0.0092 (13)	0.0137 (12)
N16	0.0273 (13)	0.0306 (13)	0.0362 (14)	0.0053 (10)	0.0134 (11)	0.0057 (11)
N17	0.0236 (12)	0.0319 (13)	0.0323 (13)	0.0070 (10)	0.0127 (10)	0.0080 (10)
N18	0.0372 (15)	0.0335 (15)	0.0428 (15)	0.0085 (12)	0.0189 (12)	0.0051 (12)
O1	0.0764 (17)	0.0423 (13)	0.0546 (15)	0.0124 (12)	0.0433 (14)	0.0078 (11)
O2	0.0458 (14)	0.0351 (13)	0.0846 (18)	0.0100 (11)	0.0297 (13)	−0.0021 (12)
O3	0.0309 (12)	0.0698 (16)	0.0575 (15)	−0.0006 (11)	0.0059 (11)	0.0339 (13)
O4	0.0755 (18)	0.0399 (14)	0.0652 (16)	−0.0047 (13)	0.0304 (14)	0.0151 (12)
O5	0.0414 (13)	0.0342 (13)	0.0815 (17)	0.0102 (10)	0.0373 (13)	0.0080 (11)
O6	0.0331 (13)	0.101 (2)	0.0672 (17)	0.0008 (13)	0.0136 (12)	0.0492 (15)
O7	0.0565 (15)	0.0387 (13)	0.0730 (17)	0.0069 (11)	0.0421 (13)	0.0057 (12)
O8	0.086 (2)	0.0591 (17)	0.096 (2)	−0.0030 (15)	0.0426 (18)	0.0341 (16)
C1	0.0311 (16)	0.0416 (18)	0.0315 (16)	0.0127 (13)	0.0126 (13)	0.0094 (13)
C2	0.0391 (18)	0.054 (2)	0.0341 (17)	0.0127 (15)	0.0202 (14)	0.0116 (15)
C3	0.0364 (17)	0.051 (2)	0.0363 (17)	0.0114 (15)	0.0187 (14)	0.0163 (15)
C4	0.0301 (16)	0.0437 (18)	0.0354 (17)	0.0109 (14)	0.0115 (14)	0.0068 (14)
C5	0.0456 (19)	0.046 (2)	0.0367 (18)	0.0130 (16)	0.0121 (15)	0.0038 (15)
C6	0.057 (2)	0.046 (2)	0.048 (2)	0.0092 (17)	0.0129 (18)	0.0082 (17)
C7	0.060 (2)	0.047 (2)	0.051 (2)	0.0144 (18)	0.0095 (19)	−0.0030 (18)
C8	0.055 (2)	0.061 (2)	0.0387 (19)	0.0179 (18)	0.0155 (17)	−0.0035 (17)
C9	0.046 (2)	0.053 (2)	0.0421 (19)	0.0146 (16)	0.0182 (16)	0.0020 (16)
C10	0.0319 (16)	0.0465 (19)	0.0346 (17)	0.0148 (14)	0.0073 (14)	0.0028 (14)
C11	0.066 (2)	0.056 (2)	0.056 (2)	0.0053 (18)	0.040 (2)	0.0210 (18)
C12	0.0362 (17)	0.0343 (16)	0.0283 (15)	0.0095 (13)	0.0116 (13)	0.0058 (12)
C13	0.0463 (19)	0.0360 (18)	0.0465 (19)	0.0189 (15)	0.0198 (16)	0.0103 (14)
C14	0.0470 (19)	0.0308 (16)	0.0407 (18)	0.0122 (14)	0.0181 (15)	0.0108 (13)
C15	0.0378 (17)	0.0344 (17)	0.0320 (16)	0.0105 (14)	0.0104 (14)	0.0085 (13)
C16	0.0417 (19)	0.047 (2)	0.047 (2)	0.0077 (16)	0.0178 (16)	0.0021 (16)
C17	0.045 (2)	0.050 (2)	0.053 (2)	−0.0001 (17)	0.0082 (17)	0.0031 (17)
C18	0.0352 (18)	0.058 (2)	0.053 (2)	0.0090 (16)	0.0125 (16)	0.0218 (18)
C19	0.053 (2)	0.063 (3)	0.085 (3)	0.013 (2)	0.040 (2)	0.003 (2)
C20	0.056 (2)	0.044 (2)	0.079 (3)	0.0047 (17)	0.037 (2)	−0.0046 (19)
C21	0.0327 (16)	0.0360 (17)	0.0353 (16)	0.0115 (13)	0.0110 (13)	0.0106 (13)
C22	0.066 (2)	0.0330 (19)	0.087 (3)	0.0145 (17)	0.033 (2)	0.0231 (18)
C23	0.0331 (16)	0.0321 (16)	0.0307 (16)	0.0093 (13)	0.0135 (13)	0.0066 (12)
C24	0.0327 (16)	0.0364 (17)	0.0314 (16)	0.0048 (13)	0.0093 (13)	0.0029 (13)
C25	0.0333 (16)	0.0300 (16)	0.0384 (17)	0.0037 (13)	0.0149 (14)	0.0008 (13)
C26	0.0369 (17)	0.0371 (17)	0.0293 (16)	0.0069 (14)	0.0111 (14)	0.0068 (13)
C27	0.0415 (18)	0.0343 (17)	0.0335 (17)	0.0056 (14)	0.0106 (14)	0.0052 (13)
C28	0.052 (2)	0.0421 (19)	0.0414 (19)	−0.0004 (16)	0.0117 (17)	0.0116 (15)
C29	0.068 (3)	0.071 (3)	0.074 (3)	0.004 (2)	0.011 (2)	0.046 (2)
C30	0.057 (3)	0.094 (3)	0.095 (3)	0.021 (2)	0.003 (2)	0.066 (3)
C31	0.039 (2)	0.065 (2)	0.070 (3)	0.0048 (17)	0.0071 (18)	0.036 (2)
C32	0.0400 (17)	0.0333 (16)	0.0283 (16)	0.0066 (14)	0.0060 (14)	0.0053 (13)
C33	0.051 (2)	0.0375 (19)	0.056 (2)	−0.0076 (16)	0.0157 (18)	0.0091 (16)
C34	0.0423 (18)	0.0388 (18)	0.0334 (17)	0.0091 (15)	0.0142 (14)	0.0067 (14)
C35	0.0239 (14)	0.0328 (16)	0.0338 (16)	0.0064 (12)	0.0120 (12)	0.0020 (12)
C36	0.0334 (17)	0.0402 (18)	0.0462 (18)	0.0174 (14)	0.0184 (15)	0.0103 (14)
C37	0.0344 (16)	0.0334 (17)	0.0424 (18)	0.0131 (13)	0.0175 (14)	0.0114 (14)
C38	0.0251 (15)	0.0385 (18)	0.0384 (17)	0.0080 (13)	0.0129 (13)	0.0020 (14)
C39	0.0316 (17)	0.057 (2)	0.0459 (19)	0.0144 (15)	0.0161 (15)	0.0154 (16)
C40	0.0415 (19)	0.058 (2)	0.057 (2)	0.0083 (17)	0.0246 (17)	0.0237 (18)
C41	0.0298 (17)	0.068 (2)	0.048 (2)	−0.0002 (16)	0.0205 (16)	−0.0007 (18)
C42	0.0247 (16)	0.059 (2)	0.0457 (19)	0.0117 (15)	0.0131 (14)	−0.0020 (16)
C43	0.0283 (16)	0.0475 (19)	0.0420 (18)	0.0103 (14)	0.0143 (14)	0.0019 (15)
C44	0.0216 (14)	0.0439 (18)	0.0317 (16)	0.0074 (13)	0.0100 (12)	0.0047 (13)
C45	0.050 (2)	0.044 (2)	0.073 (2)	0.0169 (16)	0.0302 (19)	0.0277 (18)
C46	0.0285 (15)	0.0433 (18)	0.0335 (16)	0.0087 (13)	0.0142 (13)	0.0053 (13)
C47	0.0318 (16)	0.0432 (18)	0.0314 (16)	0.0053 (14)	0.0102 (13)	0.0006 (14)
C48	0.0288 (15)	0.0310 (16)	0.0386 (17)	0.0054 (13)	0.0157 (14)	−0.0022 (13)
C49	0.0347 (17)	0.0489 (19)	0.0333 (17)	0.0060 (15)	0.0137 (14)	0.0079 (14)
C50	0.047 (2)	0.053 (2)	0.051 (2)	0.0091 (17)	0.0179 (17)	0.0181 (17)
C51	0.064 (3)	0.056 (2)	0.061 (2)	0.0037 (19)	0.025 (2)	0.0232 (19)
C52	0.070 (3)	0.061 (3)	0.068 (3)	−0.010 (2)	−0.002 (2)	0.033 (2)
C53	0.057 (3)	0.077 (3)	0.080 (3)	−0.004 (2)	−0.019 (2)	0.043 (2)
C54	0.044 (2)	0.059 (2)	0.062 (2)	−0.0079 (18)	−0.0021 (18)	0.0254 (19)
C55	0.0416 (18)	0.0386 (18)	0.0356 (17)	0.0028 (15)	0.0075 (15)	0.0060 (14)
C56	0.0437 (19)	0.0365 (18)	0.0462 (19)	0.0004 (15)	0.0133 (16)	0.0007 (15)
C57	0.0267 (15)	0.0354 (16)	0.0322 (16)	0.0078 (12)	0.0096 (13)	0.0045 (13)
C58	0.0352 (17)	0.0431 (18)	0.0338 (16)	0.0143 (14)	0.0179 (14)	0.0077 (14)
C59	0.0299 (16)	0.0437 (18)	0.0295 (15)	0.0124 (13)	0.0120 (13)	0.0099 (13)
C60	0.0317 (16)	0.0385 (18)	0.0358 (17)	0.0053 (13)	0.0120 (14)	0.0007 (13)
C61	0.054 (2)	0.042 (2)	0.048 (2)	0.0118 (16)	0.0185 (17)	0.0118 (16)
C62	0.068 (3)	0.045 (2)	0.053 (2)	0.0080 (19)	0.013 (2)	0.0171 (17)
C63	0.069 (3)	0.037 (2)	0.059 (2)	0.0176 (19)	0.004 (2)	0.0050 (18)
C64	0.064 (2)	0.048 (2)	0.067 (3)	0.0254 (19)	0.019 (2)	−0.0006 (19)
C65	0.052 (2)	0.047 (2)	0.055 (2)	0.0136 (17)	0.0226 (18)	0.0042 (17)
C66	0.0382 (17)	0.0368 (18)	0.0356 (17)	0.0106 (14)	0.0097 (14)	0.0039 (14)
C67	0.058 (2)	0.046 (2)	0.0419 (19)	0.0137 (16)	0.0291 (17)	0.0167 (15)
C68	0.0451 (19)	0.044 (2)	0.052 (2)	0.0092 (16)	0.0236 (17)	0.0152 (16)
O9	0.0560 (16)	0.0809 (18)	0.0526 (15)	0.0138 (13)	0.0326 (13)	0.0089 (13)
C69	0.064 (3)	0.139 (5)	0.077 (3)	0.026 (3)	0.026 (3)	0.047 (3)
C70	0.052 (2)	0.115 (4)	0.057 (3)	0.015 (2)	0.024 (2)	0.010 (2)
C71	0.062 (2)	0.060 (2)	0.065 (3)	0.0085 (19)	0.036 (2)	0.018 (2)
C72	0.060 (3)	0.180 (5)	0.074 (3)	0.027 (3)	0.031 (2)	0.063 (3)
O10	0.089 (2)	0.0416 (15)	0.084 (2)	−0.0029 (15)	0.0225 (18)	−0.0018 (14)
C73	0.075 (3)	0.065 (3)	0.101 (4)	0.013 (2)	0.012 (3)	0.014 (3)
C74	0.086 (3)	0.077 (3)	0.086 (3)	−0.013 (3)	0.047 (3)	0.006 (3)
C75	0.104 (4)	0.068 (3)	0.094 (4)	0.009 (3)	0.010 (3)	0.026 (3)
C76	0.055 (3)	0.127 (5)	0.101 (4)	0.003 (3)	0.005 (3)	0.016 (3)
O11	0.0478 (13)	0.0681 (15)	0.0564 (14)	−0.0019 (11)	0.0186 (11)	0.0071 (12)
C77	0.071 (2)	0.098 (3)	0.076 (2)	0.009 (2)	0.0373 (19)	0.006 (2)
C78	0.104 (3)	0.112 (3)	0.107 (3)	−0.029 (2)	0.049 (2)	0.011 (3)
C79	0.111 (3)	0.091 (3)	0.076 (2)	−0.027 (2)	0.011 (2)	0.013 (2)
C80	0.070 (2)	0.072 (2)	0.059 (2)	0.0055 (18)	0.0168 (18)	0.0044 (17)
O12	0.0860 (17)	0.0415 (13)	0.0773 (16)	0.0083 (12)	0.0503 (14)	−0.0014 (12)
C81	0.108 (3)	0.048 (2)	0.083 (2)	−0.0036 (19)	0.046 (2)	−0.0001 (18)
C82	0.156 (3)	0.067 (2)	0.093 (3)	−0.024 (2)	0.059 (2)	−0.020 (2)
C83	0.138 (3)	0.077 (3)	0.092 (3)	−0.007 (2)	0.058 (2)	−0.025 (2)
C84	0.109 (3)	0.074 (2)	0.090 (3)	−0.004 (2)	0.060 (2)	−0.025 (2)
O13	0.0426 (13)	0.0536 (14)	0.0469 (14)	−0.0068 (11)	0.0141 (11)	0.0029 (11)
C85	0.061 (2)	0.082 (3)	0.060 (2)	0.011 (2)	0.029 (2)	0.009 (2)
C86	0.078 (3)	0.063 (3)	0.072 (3)	−0.014 (2)	0.020 (2)	0.011 (2)
C87	0.099 (3)	0.051 (2)	0.060 (3)	−0.004 (2)	0.012 (2)	0.015 (2)
C88	0.066 (3)	0.060 (2)	0.054 (2)	0.019 (2)	0.018 (2)	0.0082 (19)
O14	0.0544 (15)	0.0556 (15)	0.0548 (15)	−0.0017 (12)	0.0299 (13)	−0.0036 (12)
C89	0.057 (2)	0.072 (3)	0.043 (2)	0.005 (2)	0.0179 (18)	−0.0051 (18)
C90	0.112 (4)	0.068 (3)	0.082 (3)	0.005 (3)	0.043 (3)	0.019 (3)
C91	0.086 (3)	0.063 (3)	0.137 (5)	−0.011 (3)	0.052 (3)	0.006 (3)
C92	0.050 (2)	0.093 (3)	0.059 (3)	0.003 (2)	0.010 (2)	−0.013 (2)

Geometric parameters (Å, º)

Cu1—C34	1.793 (3)	C40—H40	0.9500
Cu1—N1	2.078 (2)	C41—C42	1.370 (4)
Cu1—N4	2.062 (2)	C41—H41	0.9500
Cu1—N7	2.069 (2)	C42—C43	1.383 (4)
Cu2—C68	1.798 (3)	C42—H42	0.9500
Cu2—N10	2.068 (2)	C43—C44	1.395 (4)
Cu2—N13	2.063 (2)	C43—H43	0.9500
Cu2—N16	2.075 (2)	C45—H45A	0.9800
B1—N2	1.544 (4)	C45—H45B	0.9800
B1—N5	1.548 (4)	C45—H45C	0.9800
B1—N8	1.556 (4)	C46—C47	1.398 (4)
B1—H1	1.0000	C46—C49	1.491 (4)
B2—N11	1.548 (4)	C47—C48	1.384 (4)
B2—N17	1.551 (4)	C47—H47	0.9500
B2—N14	1.552 (4)	C48—C56	1.493 (4)
B2—H2	1.0000	C50—C51	1.385 (4)
N1—C1	1.340 (3)	C50—C55	1.391 (4)
N1—N2	1.364 (3)	C50—H50	0.9500
N2—C3	1.363 (3)	C51—C52	1.365 (5)
N3—C4	1.363 (4)	C51—H51	0.9500
N3—C10	1.420 (4)	C52—C53	1.381 (5)
N3—H3A	0.817 (18)	C52—H52	0.9500
N4—C12	1.339 (3)	C53—C54	1.393 (5)
N4—N5	1.364 (3)	C53—H53	0.9500
N5—C14	1.355 (3)	C54—C55	1.386 (4)
N6—C15	1.358 (4)	C54—H54	0.9500
N6—C21	1.419 (4)	C56—H56A	0.9800
N6—H6A	0.812 (18)	C56—H56B	0.9800
N7—C23	1.338 (3)	C56—H56C	0.9800
N7—N8	1.364 (3)	C57—C58	1.389 (4)
N8—C25	1.359 (3)	C57—C60	1.497 (4)
N9—C26	1.352 (4)	C58—C59	1.373 (4)
N9—C32	1.421 (4)	C58—H58	0.9500
N9—H9A	0.816 (18)	C59—C67	1.493 (4)
N10—C35	1.344 (3)	C61—C66	1.387 (4)
N10—N11	1.364 (3)	C61—C62	1.397 (4)
N11—C37	1.356 (3)	C61—H61	0.9500
N12—C38	1.358 (3)	C62—C63	1.374 (5)
N12—C44	1.414 (3)	C62—H62	0.9500
N12—H12A	0.814 (17)	C63—C64	1.377 (5)
N13—C46	1.341 (3)	C63—H63	0.9500
N13—N14	1.364 (3)	C64—C65	1.381 (4)
N14—C48	1.362 (3)	C64—H64	0.9500
N15—C49	1.355 (4)	C65—C66	1.389 (4)
N15—C55	1.413 (4)	C65—H65	0.9500
N15—H15A	0.827 (18)	C67—H67A	0.9800
N16—C57	1.342 (3)	C67—H67B	0.9800
N16—N17	1.362 (3)	C67—H67C	0.9800
N17—C59	1.364 (3)	O9—C72	1.394 (4)
N18—C60	1.360 (4)	O9—C69	1.427 (4)
N18—C66	1.418 (4)	C69—C70	1.449 (5)
N18—H18A	0.813 (17)	C69—H69A	0.9900
O1—C4	1.217 (3)	C69—H69B	0.9900
O2—C15	1.220 (3)	C70—C71	1.487 (5)
O3—C26	1.221 (3)	C70—H70A	0.9900
O4—C34	1.134 (3)	C70—H70B	0.9900
O5—C38	1.217 (3)	C71—C72	1.477 (5)
O6—C49	1.219 (3)	C71—H71A	0.9900
O7—C60	1.222 (3)	C71—H71B	0.9900
O8—C68	1.128 (4)	C72—H72A	0.9900
C1—C2	1.398 (4)	C72—H72B	0.9900
C1—C4	1.490 (4)	O10—C73	1.389 (5)
C2—C3	1.369 (4)	O10—C76	1.441 (5)
C2—H2A	0.9500	C73—C74	1.472 (5)
C3—C11	1.498 (4)	C73—H73A	0.9900
C5—C6	1.389 (4)	C73—H73B	0.9900
C5—C10	1.391 (4)	C74—C75	1.467 (6)
C5—H5	0.9500	C74—H74A	0.9900
C6—C7	1.382 (5)	C74—H74B	0.9900
C6—H6	0.9500	C75—C76	1.501 (6)
C7—C8	1.379 (5)	C75—H75A	0.9900
C7—H7	0.9500	C75—H75B	0.9900
C8—C9	1.380 (4)	C76—H76A	0.9900
C8—H8	0.9500	C76—H76B	0.9900
C9—C10	1.390 (4)	O11—C80	1.417 (4)
C9—H9	0.9500	O11—C77	1.427 (4)
C11—H11A	0.9800	C77—C78	1.488 (6)
C11—H11B	0.9800	C77—H77A	0.9900
C11—H11C	0.9800	C77—H77B	0.9900
C12—C13	1.389 (4)	C78—C79	1.454 (6)
C12—C15	1.496 (4)	C78—H78A	0.9900
C13—C14	1.382 (4)	C78—H78B	0.9900
C13—H13	0.9500	C79—C80	1.458 (5)
C14—C22	1.505 (4)	C79—H79A	0.9900
C16—C21	1.366 (4)	C79—H79B	0.9900
C16—C17	1.391 (4)	C80—H80A	0.9900
C16—H16	0.9500	C80—H80B	0.9900
C17—C18	1.370 (5)	O12—C84	1.390 (4)
C17—H17	0.9500	O12—C81	1.429 (4)
C18—C19	1.365 (5)	C81—C82	1.504 (6)
C18—H18	0.9500	C81—H81A	0.9900
C19—C20	1.378 (5)	C81—H81B	0.9900
C19—H19	0.9500	C82—C83	1.428 (6)
C20—C21	1.392 (4)	C82—H82A	0.9900
C20—H20	0.9500	C82—H82B	0.9900
C22—H22A	0.9800	C83—C84	1.483 (6)
C22—H22B	0.9800	C83—H83A	0.9900
C22—H22C	0.9800	C83—H83B	0.9900
C23—C24	1.403 (4)	C84—H84A	0.9900
C23—C26	1.494 (4)	C84—H84B	0.9900
C24—C25	1.380 (4)	O13—C88	1.421 (4)
C24—H24	0.9500	O13—C85	1.434 (4)
C25—C33	1.498 (4)	C85—C86	1.519 (5)
C27—C28	1.385 (4)	C85—H85A	0.9900
C27—C32	1.388 (4)	C85—H85B	0.9900
C27—H27	0.9500	C86—C87	1.495 (5)
C28—C29	1.365 (5)	C86—H86A	0.9900
C28—H28	0.9500	C86—H86B	0.9900
C29—C30	1.387 (5)	C87—C88	1.472 (5)
C29—H29	0.9500	C87—H87A	0.9900
C30—C31	1.389 (5)	C87—H87B	0.9900
C30—H30	0.9500	C88—H88A	0.9900
C31—C32	1.376 (4)	C88—H88B	0.9900
C31—H31	0.9500	O14—C92	1.417 (4)
C33—H33A	0.9800	O14—C89	1.420 (4)
C33—H33B	0.9800	C89—C90	1.474 (5)
C33—H33C	0.9800	C89—H89A	0.9900
C35—C36	1.391 (4)	C89—H89B	0.9900
C35—C38	1.493 (4)	C90—C91	1.505 (6)
C36—C37	1.378 (4)	C90—H90A	0.9900
C36—H36	0.9500	C90—H90B	0.9900
C37—C45	1.497 (4)	C91—C92	1.497 (6)
C39—C44	1.381 (4)	C91—H91A	0.9900
C39—C40	1.393 (4)	C91—H91B	0.9900
C39—H39	0.9500	C92—H92A	0.9900
C40—C41	1.376 (4)	C92—H92B	0.9900
C34—Cu1—N4	126.82 (12)	N13—C46—C47	110.1 (3)
C34—Cu1—N7	124.53 (11)	N13—C46—C49	117.9 (3)
N4—Cu1—N7	90.05 (9)	C47—C46—C49	131.9 (3)
C34—Cu1—N1	124.14 (11)	C48—C47—C46	105.8 (3)
N4—Cu1—N1	91.36 (9)	C48—C47—H47	127.1
N7—Cu1—N1	88.90 (9)	C46—C47—H47	127.1
C68—Cu2—N13	127.77 (13)	N14—C48—C47	107.2 (2)
C68—Cu2—N10	124.04 (12)	N14—C48—C56	123.4 (3)
N13—Cu2—N10	89.94 (9)	C47—C48—C56	129.5 (3)
C68—Cu2—N16	124.63 (12)	O6—C49—N15	124.1 (3)
N13—Cu2—N16	87.90 (9)	O6—C49—C46	120.9 (3)
N10—Cu2—N16	91.29 (9)	N15—C49—C46	114.9 (3)
N2—B1—N5	109.7 (2)	C51—C50—C55	120.0 (3)
N2—B1—N8	108.0 (2)	C51—C50—H50	120.0
N5—B1—N8	109.8 (2)	C55—C50—H50	120.0
N2—B1—H1	109.8	C52—C51—C50	121.2 (4)
N5—B1—H1	109.8	C52—C51—H51	119.4
N8—B1—H1	109.8	C50—C51—H51	119.4
N11—B2—N17	108.9 (2)	C51—C52—C53	119.6 (4)
N11—B2—N14	109.0 (2)	C51—C52—H52	120.2
N17—B2—N14	109.4 (2)	C53—C52—H52	120.2
N11—B2—H2	109.8	C52—C53—C54	119.7 (4)
N17—B2—H2	109.8	C52—C53—H53	120.2
N14—B2—H2	109.8	C54—C53—H53	120.2
C1—N1—N2	106.3 (2)	C55—C54—C53	120.9 (3)
C1—N1—Cu1	138.6 (2)	C55—C54—H54	119.6
N2—N1—Cu1	114.93 (16)	C53—C54—H54	119.6
C3—N2—N1	110.1 (2)	C54—C55—C50	118.5 (3)
C3—N2—B1	130.1 (2)	C54—C55—N15	117.7 (3)
N1—N2—B1	119.7 (2)	C50—C55—N15	123.8 (3)
C4—N3—C10	127.7 (3)	C48—C56—H56A	109.5
C4—N3—H3A	118 (2)	C48—C56—H56B	109.5
C10—N3—H3A	114 (2)	H56A—C56—H56B	109.5
C12—N4—N5	106.1 (2)	C48—C56—H56C	109.5
C12—N4—Cu1	138.38 (19)	H56A—C56—H56C	109.5
N5—N4—Cu1	115.42 (17)	H56B—C56—H56C	109.5
C14—N5—N4	110.2 (2)	N16—C57—C58	110.3 (3)
C14—N5—B1	130.2 (2)	N16—C57—C60	118.8 (2)
N4—N5—B1	119.6 (2)	C58—C57—C60	130.9 (3)
C15—N6—C21	127.1 (2)	C59—C58—C57	106.2 (2)
C15—N6—H6A	114 (2)	C59—C58—H58	126.9
C21—N6—H6A	119 (2)	C57—C58—H58	126.9
C23—N7—N8	106.4 (2)	N17—C59—C58	107.2 (2)
C23—N7—Cu1	137.44 (19)	N17—C59—C67	123.1 (3)
N8—N7—Cu1	115.38 (17)	C58—C59—C67	129.7 (3)
C25—N8—N7	110.1 (2)	O7—C60—N18	124.1 (3)
C25—N8—B1	130.5 (2)	O7—C60—C57	121.7 (3)
N7—N8—B1	119.3 (2)	N18—C60—C57	114.3 (3)
C26—N9—C32	127.3 (2)	C66—C61—C62	119.2 (3)
C26—N9—H9A	119 (2)	C66—C61—H61	120.4
C32—N9—H9A	113 (2)	C62—C61—H61	120.4
C35—N10—N11	105.3 (2)	C63—C62—C61	121.4 (3)
C35—N10—Cu2	138.35 (19)	C63—C62—H62	119.3
N11—N10—Cu2	116.30 (16)	C61—C62—H62	119.3
C37—N11—N10	111.1 (2)	C62—C63—C64	119.0 (3)
C37—N11—B2	130.0 (2)	C62—C63—H63	120.5
N10—N11—B2	118.9 (2)	C64—C63—H63	120.5
C38—N12—C44	127.2 (3)	C63—C64—C65	120.6 (3)
C38—N12—H12A	119 (2)	C63—C64—H64	119.7
C44—N12—H12A	114 (2)	C65—C64—H64	119.7
C46—N13—N14	106.5 (2)	C64—C65—C66	120.7 (3)
C46—N13—Cu2	137.5 (2)	C64—C65—H65	119.7
N14—N13—Cu2	115.92 (17)	C66—C65—H65	119.7
C48—N14—N13	110.4 (2)	C61—C66—C65	119.2 (3)
C48—N14—B2	130.2 (2)	C61—C66—N18	123.6 (3)
N13—N14—B2	119.4 (2)	C65—C66—N18	117.2 (3)
C49—N15—C55	127.6 (3)	C59—C67—H67A	109.5
C49—N15—H15A	122 (2)	C59—C67—H67B	109.5
C55—N15—H15A	110 (2)	H67A—C67—H67B	109.5
C57—N16—N17	106.2 (2)	C59—C67—H67C	109.5
C57—N16—Cu2	138.52 (19)	H67A—C67—H67C	109.5
N17—N16—Cu2	115.28 (16)	H67B—C67—H67C	109.5
N16—N17—C59	110.2 (2)	O8—C68—Cu2	178.8 (3)
N16—N17—B2	119.8 (2)	C72—O9—C69	108.6 (3)
C59—N17—B2	129.8 (2)	O9—C69—C70	108.4 (3)
C60—N18—C66	127.5 (3)	O9—C69—H69A	110.0
C60—N18—H18A	115 (2)	C70—C69—H69A	110.0
C66—N18—H18A	117 (2)	O9—C69—H69B	110.0
N1—C1—C2	110.1 (3)	C70—C69—H69B	110.0
N1—C1—C4	118.2 (2)	H69A—C69—H69B	108.4
C2—C1—C4	131.5 (3)	C69—C70—C71	106.4 (3)
C3—C2—C1	105.9 (3)	C69—C70—H70A	110.5
C3—C2—H2A	127.0	C71—C70—H70A	110.5
C1—C2—H2A	127.0	C69—C70—H70B	110.5
N2—C3—C2	107.5 (3)	C71—C70—H70B	110.5
N2—C3—C11	122.6 (3)	H70A—C70—H70B	108.6
C2—C3—C11	129.9 (3)	C72—C71—C70	103.7 (3)
O1—C4—N3	123.3 (3)	C72—C71—H71A	111.0
O1—C4—C1	121.9 (3)	C70—C71—H71A	111.0
N3—C4—C1	114.8 (3)	C72—C71—H71B	111.0
C6—C5—C10	119.2 (3)	C70—C71—H71B	111.0
C6—C5—H5	120.4	H71A—C71—H71B	109.0
C10—C5—H5	120.4	O9—C72—C71	109.5 (3)
C7—C6—C5	121.4 (3)	O9—C72—H72A	109.8
C7—C6—H6	119.3	C71—C72—H72A	109.8
C5—C6—H6	119.3	O9—C72—H72B	109.8
C8—C7—C6	119.1 (3)	C71—C72—H72B	109.8
C8—C7—H7	120.5	H72A—C72—H72B	108.2
C6—C7—H7	120.5	C73—O10—C76	102.5 (3)
C7—C8—C9	120.4 (3)	O10—C73—C74	106.0 (4)
C7—C8—H8	119.8	O10—C73—H73A	110.5
C9—C8—H8	119.8	C74—C73—H73A	110.5
C8—C9—C10	120.6 (3)	O10—C73—H73B	110.5
C8—C9—H9	119.7	C74—C73—H73B	110.5
C10—C9—H9	119.7	H73A—C73—H73B	108.7
C9—C10—C5	119.3 (3)	C75—C74—C73	104.6 (4)
C9—C10—N3	116.7 (3)	C75—C74—H74A	110.8
C5—C10—N3	124.0 (3)	C73—C74—H74A	110.8
C3—C11—H11A	109.5	C75—C74—H74B	110.8
C3—C11—H11B	109.5	C73—C74—H74B	110.8
H11A—C11—H11B	109.5	H74A—C74—H74B	108.9
C3—C11—H11C	109.5	C74—C75—C76	104.1 (4)
H11A—C11—H11C	109.5	C74—C75—H75A	110.9
H11B—C11—H11C	109.5	C76—C75—H75A	110.9
N4—C12—C13	110.6 (3)	C74—C75—H75B	110.9
N4—C12—C15	119.5 (2)	C76—C75—H75B	110.9
C13—C12—C15	129.7 (3)	H75A—C75—H75B	109.0
C14—C13—C12	105.4 (3)	O10—C76—C75	104.8 (3)
C14—C13—H13	127.3	O10—C76—H76A	110.8
C12—C13—H13	127.3	C75—C76—H76A	110.8
N5—C14—C13	107.6 (3)	O10—C76—H76B	110.8
N5—C14—C22	122.7 (3)	C75—C76—H76B	110.8
C13—C14—C22	129.6 (3)	H76A—C76—H76B	108.9
O2—C15—N6	123.9 (3)	C80—O11—C77	109.1 (3)
O2—C15—C12	121.2 (3)	O11—C77—C78	104.5 (3)
N6—C15—C12	114.9 (3)	O11—C77—H77A	110.9
C21—C16—C17	120.2 (3)	C78—C77—H77A	110.9
C21—C16—H16	119.9	O11—C77—H77B	110.9
C17—C16—H16	119.9	C78—C77—H77B	110.9
C18—C17—C16	121.4 (3)	H77A—C77—H77B	108.9
C18—C17—H17	119.3	C79—C78—C77	106.1 (4)
C16—C17—H17	119.3	C79—C78—H78A	110.5
C19—C18—C17	118.4 (3)	C77—C78—H78A	110.5
C19—C18—H18	120.8	C79—C78—H78B	110.5
C17—C18—H18	120.8	C77—C78—H78B	110.5
C18—C19—C20	121.0 (3)	H78A—C78—H78B	108.7
C18—C19—H19	119.5	C78—C79—C80	106.7 (4)
C20—C19—H19	119.5	C78—C79—H79A	110.4
C19—C20—C21	120.7 (3)	C80—C79—H79A	110.4
C19—C20—H20	119.7	C78—C79—H79B	110.4
C21—C20—H20	119.7	C80—C79—H79B	110.4
C16—C21—C20	118.3 (3)	H79A—C79—H79B	108.6
C16—C21—N6	124.0 (3)	O11—C80—C79	107.7 (3)
C20—C21—N6	117.6 (3)	O11—C80—H80A	110.2
C14—C22—H22A	109.5	C79—C80—H80A	110.2
C14—C22—H22B	109.5	O11—C80—H80B	110.2
H22A—C22—H22B	109.5	C79—C80—H80B	110.2
C14—C22—H22C	109.5	H80A—C80—H80B	108.5
H22A—C22—H22C	109.5	C84—O12—C81	108.1 (3)
H22B—C22—H22C	109.5	O12—C81—C82	106.0 (3)
N7—C23—C24	110.5 (2)	O12—C81—H81A	110.5
N7—C23—C26	118.2 (2)	C82—C81—H81A	110.5
C24—C23—C26	131.2 (3)	O12—C81—H81B	110.5
C25—C24—C23	105.1 (3)	C82—C81—H81B	110.5
C25—C24—H24	127.5	H81A—C81—H81B	108.7
C23—C24—H24	127.5	C83—C82—C81	107.4 (4)
N8—C25—C24	107.9 (2)	C83—C82—H82A	110.2
N8—C25—C33	122.8 (3)	C81—C82—H82A	110.2
C24—C25—C33	129.2 (3)	C83—C82—H82B	110.2
O3—C26—N9	124.3 (3)	C81—C82—H82B	110.2
O3—C26—C23	120.9 (3)	H82A—C82—H82B	108.5
N9—C26—C23	114.8 (3)	C82—C83—C84	103.6 (4)
C28—C27—C32	119.9 (3)	C82—C83—H83A	111.1
C28—C27—H27	120.0	C84—C83—H83A	111.1
C32—C27—H27	120.0	C82—C83—H83B	111.0
C29—C28—C27	121.0 (3)	C84—C83—H83B	111.1
C29—C28—H28	119.5	H83A—C83—H83B	109.0
C27—C28—H28	119.5	O12—C84—C83	108.5 (4)
C28—C29—C30	119.4 (3)	O12—C84—H84A	110.0
C28—C29—H29	120.3	C83—C84—H84A	110.0
C30—C29—H29	120.3	O12—C84—H84B	110.0
C29—C30—C31	120.0 (4)	C83—C84—H84B	110.0
C29—C30—H30	120.0	H84A—C84—H84B	108.4
C31—C30—H30	120.0	C88—O13—C85	109.9 (3)
C32—C31—C30	120.5 (3)	O13—C85—C86	104.4 (3)
C32—C31—H31	119.8	O13—C85—H85A	110.9
C30—C31—H31	119.8	C86—C85—H85A	110.9
C31—C32—C27	119.2 (3)	O13—C85—H85B	110.9
C31—C32—N9	117.6 (3)	C86—C85—H85B	110.9
C27—C32—N9	123.2 (3)	H85A—C85—H85B	108.9
C25—C33—H33A	109.5	C87—C86—C85	102.5 (3)
C25—C33—H33B	109.5	C87—C86—H86A	111.3
H33A—C33—H33B	109.5	C85—C86—H86A	111.3
C25—C33—H33C	109.5	C87—C86—H86B	111.3
H33A—C33—H33C	109.5	C85—C86—H86B	111.3
H33B—C33—H33C	109.5	H86A—C86—H86B	109.2
O4—C34—Cu1	177.8 (3)	C88—C87—C86	103.8 (3)
N10—C35—C36	110.8 (2)	C88—C87—H87A	111.0
N10—C35—C38	119.4 (2)	C86—C87—H87A	111.0
C36—C35—C38	129.8 (3)	C88—C87—H87B	111.0
C37—C36—C35	105.7 (3)	C86—C87—H87B	111.0
C37—C36—H36	127.1	H87A—C87—H87B	109.0
C35—C36—H36	127.1	O13—C88—C87	107.3 (3)
N11—C37—C36	107.1 (2)	O13—C88—H88A	110.3
N11—C37—C45	123.5 (3)	C87—C88—H88A	110.3
C36—C37—C45	129.4 (3)	O13—C88—H88B	110.3
O5—C38—N12	124.5 (3)	C87—C88—H88B	110.3
O5—C38—C35	123.2 (2)	H88A—C88—H88B	108.5
N12—C38—C35	112.3 (3)	C92—O14—C89	106.4 (3)
C44—C39—C40	119.0 (3)	O14—C89—C90	106.7 (3)
C44—C39—H39	120.5	O14—C89—H89A	110.4
C40—C39—H39	120.5	C90—C89—H89A	110.4
C41—C40—C39	121.5 (3)	O14—C89—H89B	110.4
C41—C40—H40	119.2	C90—C89—H89B	110.4
C39—C40—H40	119.2	H89A—C89—H89B	108.6
C42—C41—C40	119.1 (3)	C89—C90—C91	104.8 (3)
C42—C41—H41	120.5	C89—C90—H90A	110.8
C40—C41—H41	120.5	C91—C90—H90A	110.8
C41—C42—C43	120.7 (3)	C89—C90—H90B	110.8
C41—C42—H42	119.7	C91—C90—H90B	110.8
C43—C42—H42	119.7	H90A—C90—H90B	108.9
C42—C43—C44	120.1 (3)	C92—C91—C90	105.1 (3)
C42—C43—H43	119.9	C92—C91—H91A	110.7
C44—C43—H43	119.9	C90—C91—H91A	110.7
C39—C44—C43	119.5 (3)	C92—C91—H91B	110.7
C39—C44—N12	123.7 (3)	C90—C91—H91B	110.7
C43—C44—N12	116.8 (3)	H91A—C91—H91B	108.8
C37—C45—H45A	109.5	O14—C92—C91	106.2 (3)
C37—C45—H45B	109.5	O14—C92—H92A	110.5
H45A—C45—H45B	109.5	C91—C92—H92A	110.5
C37—C45—H45C	109.5	O14—C92—H92B	110.5
H45A—C45—H45C	109.5	C91—C92—H92B	110.5
H45B—C45—H45C	109.5	H92A—C92—H92B	108.7
C34—Cu1—N1—C1	3.7 (3)	Cu1—N7—C23—C24	168.8 (2)
N4—Cu1—N1—C1	−134.1 (3)	N8—N7—C23—C26	177.1 (2)
N7—Cu1—N1—C1	135.9 (3)	Cu1—N7—C23—C26	−14.0 (4)
C34—Cu1—N1—N2	178.08 (18)	N7—C23—C24—C25	0.0 (3)
N4—Cu1—N1—N2	40.31 (18)	C26—C23—C24—C25	−176.8 (3)
N7—Cu1—N1—N2	−49.71 (18)	N7—N8—C25—C24	−0.1 (3)
C1—N1—N2—C3	−0.2 (3)	B1—N8—C25—C24	−176.5 (3)
Cu1—N1—N2—C3	−176.33 (18)	N7—N8—C25—C33	177.3 (3)
C1—N1—N2—B1	−177.5 (2)	B1—N8—C25—C33	0.9 (5)
Cu1—N1—N2—B1	6.4 (3)	C23—C24—C25—N8	0.1 (3)
N5—B1—N2—C3	120.0 (3)	C23—C24—C25—C33	−177.1 (3)
N8—B1—N2—C3	−120.4 (3)	C32—N9—C26—O3	−2.0 (5)
N5—B1—N2—N1	−63.4 (3)	C32—N9—C26—C23	177.6 (3)
N8—B1—N2—N1	56.3 (3)	N7—C23—C26—O3	−24.3 (4)
C34—Cu1—N4—C12	1.9 (3)	C24—C23—C26—O3	152.3 (3)
N7—Cu1—N4—C12	−133.2 (3)	N7—C23—C26—N9	156.0 (3)
N1—Cu1—N4—C12	137.9 (3)	C24—C23—C26—N9	−27.4 (4)
C34—Cu1—N4—N5	178.81 (18)	C32—C27—C28—C29	0.4 (5)
N7—Cu1—N4—N5	43.69 (18)	C27—C28—C29—C30	−1.1 (6)
N1—Cu1—N4—N5	−45.22 (18)	C28—C29—C30—C31	0.5 (7)
C12—N4—N5—C14	−0.9 (3)	C29—C30—C31—C32	0.6 (7)
Cu1—N4—N5—C14	−178.78 (18)	C30—C31—C32—C27	−1.3 (5)
C12—N4—N5—B1	−179.3 (2)	C30—C31—C32—N9	178.2 (4)
Cu1—N4—N5—B1	2.9 (3)	C28—C27—C32—C31	0.7 (5)
N2—B1—N5—C14	−120.4 (3)	C28—C27—C32—N9	−178.7 (3)
N8—B1—N5—C14	121.0 (3)	C26—N9—C32—C31	172.3 (3)
N2—B1—N5—N4	57.5 (3)	C26—N9—C32—C27	−8.2 (5)
N8—B1—N5—N4	−61.0 (3)	N11—N10—C35—C36	0.2 (3)
C34—Cu1—N7—C23	7.0 (3)	Cu2—N10—C35—C36	178.5 (2)
N4—Cu1—N7—C23	143.7 (3)	N11—N10—C35—C38	−177.9 (2)
N1—Cu1—N7—C23	−124.9 (3)	Cu2—N10—C35—C38	0.4 (4)
C34—Cu1—N7—N8	175.19 (18)	N10—C35—C36—C37	−0.1 (3)
N4—Cu1—N7—N8	−48.09 (18)	C38—C35—C36—C37	177.8 (3)
N1—Cu1—N7—N8	43.27 (18)	N10—N11—C37—C36	0.1 (3)
C23—N7—N8—C25	0.2 (3)	B2—N11—C37—C36	−177.8 (3)
Cu1—N7—N8—C25	−171.56 (17)	N10—N11—C37—C45	179.8 (3)
C23—N7—N8—B1	177.0 (2)	B2—N11—C37—C45	1.8 (5)
Cu1—N7—N8—B1	5.3 (3)	C35—C36—C37—N11	0.0 (3)
N2—B1—N8—C25	112.1 (3)	C35—C36—C37—C45	−179.7 (3)
N5—B1—N8—C25	−128.3 (3)	C44—N12—C38—O5	−2.6 (5)
N2—B1—N8—N7	−64.0 (3)	C44—N12—C38—C35	176.5 (3)
N5—B1—N8—N7	55.6 (3)	N10—C35—C38—O5	−23.9 (4)
C68—Cu2—N10—C35	4.4 (3)	C36—C35—C38—O5	158.4 (3)
N13—Cu2—N10—C35	−133.2 (3)	N10—C35—C38—N12	157.0 (3)
N16—Cu2—N10—C35	138.9 (3)	C36—C35—C38—N12	−20.7 (4)
C68—Cu2—N10—N11	−177.40 (19)	C44—C39—C40—C41	0.0 (5)
N13—Cu2—N10—N11	45.01 (18)	C39—C40—C41—C42	0.1 (5)
N16—Cu2—N10—N11	−42.88 (18)	C40—C41—C42—C43	0.1 (5)
C35—N10—N11—C37	−0.2 (3)	C41—C42—C43—C44	−0.4 (5)
Cu2—N10—N11—C37	−178.97 (18)	C40—C39—C44—C43	−0.4 (4)
C35—N10—N11—B2	178.0 (2)	C40—C39—C44—N12	179.2 (3)
Cu2—N10—N11—B2	−0.7 (3)	C42—C43—C44—C39	0.6 (4)
N17—B2—N11—C37	−122.0 (3)	C42—C43—C44—N12	−179.0 (3)
N14—B2—N11—C37	118.7 (3)	C38—N12—C44—C39	18.4 (5)
N17—B2—N11—N10	60.1 (3)	C38—N12—C44—C43	−162.0 (3)
N14—B2—N11—N10	−59.1 (3)	N14—N13—C46—C47	1.1 (3)
C68—Cu2—N13—C46	3.7 (3)	Cu2—N13—C46—C47	179.4 (2)
N10—Cu2—N13—C46	138.7 (3)	N14—N13—C46—C49	179.6 (2)
N16—Cu2—N13—C46	−130.0 (3)	Cu2—N13—C46—C49	−2.1 (4)
C68—Cu2—N13—N14	−178.18 (18)	N13—C46—C47—C48	−0.4 (3)
N10—Cu2—N13—N14	−43.17 (18)	C49—C46—C47—C48	−178.6 (3)
N16—Cu2—N13—N14	48.12 (18)	N13—N14—C48—C47	1.2 (3)
C46—N13—N14—C48	−1.5 (3)	B2—N14—C48—C47	−176.3 (3)
Cu2—N13—N14—C48	179.84 (16)	N13—N14—C48—C56	−179.2 (2)
C46—N13—N14—B2	176.4 (2)	B2—N14—C48—C56	3.2 (4)
Cu2—N13—N14—B2	−2.3 (3)	C46—C47—C48—N14	−0.5 (3)
N11—B2—N14—C48	−121.3 (3)	C46—C47—C48—C56	180.0 (3)
N17—B2—N14—C48	119.7 (3)	C55—N15—C49—O6	1.8 (5)
N11—B2—N14—N13	61.3 (3)	C55—N15—C49—C46	−177.0 (3)
N17—B2—N14—N13	−57.6 (3)	N13—C46—C49—O6	−34.7 (4)
C68—Cu2—N16—C57	−3.9 (3)	C47—C46—C49—O6	143.5 (3)
N13—Cu2—N16—C57	132.1 (3)	N13—C46—C49—N15	144.2 (3)
N10—Cu2—N16—C57	−138.0 (3)	C47—C46—C49—N15	−37.6 (5)
C68—Cu2—N16—N17	173.81 (18)	C55—C50—C51—C52	−1.3 (6)
N13—Cu2—N16—N17	−50.17 (18)	C50—C51—C52—C53	−0.2 (6)
N10—Cu2—N16—N17	39.71 (18)	C51—C52—C53—C54	0.4 (7)
C57—N16—N17—C59	0.7 (3)	C52—C53—C54—C55	0.8 (7)
Cu2—N16—N17—C59	−177.73 (17)	C53—C54—C55—C50	−2.1 (6)
C57—N16—N17—B2	−175.4 (2)	C53—C54—C55—N15	179.5 (4)
Cu2—N16—N17—B2	6.2 (3)	C51—C50—C55—C54	2.4 (5)
N11—B2—N17—N16	−64.0 (3)	C51—C50—C55—N15	−179.4 (3)
N14—B2—N17—N16	55.1 (3)	C49—N15—C55—C54	173.5 (3)
N11—B2—N17—C59	120.9 (3)	C49—N15—C55—C50	−4.7 (5)
N14—B2—N17—C59	−120.1 (3)	N17—N16—C57—C58	−0.6 (3)
N2—N1—C1—C2	−0.3 (3)	Cu2—N16—C57—C58	177.2 (2)
Cu1—N1—C1—C2	174.4 (2)	N17—N16—C57—C60	177.8 (2)
N2—N1—C1—C4	176.4 (2)	Cu2—N16—C57—C60	−4.4 (4)
Cu1—N1—C1—C4	−8.9 (4)	N16—C57—C58—C59	0.3 (3)
N1—C1—C2—C3	0.6 (3)	C60—C57—C58—C59	−177.8 (3)
C4—C1—C2—C3	−175.4 (3)	N16—N17—C59—C58	−0.5 (3)
N1—N2—C3—C2	0.6 (3)	B2—N17—C59—C58	175.0 (3)
B1—N2—C3—C2	177.5 (3)	N16—N17—C59—C67	179.7 (2)
N1—N2—C3—C11	−179.3 (3)	B2—N17—C59—C67	−4.8 (4)
B1—N2—C3—C11	−2.4 (5)	C57—C58—C59—N17	0.2 (3)
C1—C2—C3—N2	−0.7 (3)	C57—C58—C59—C67	180.0 (3)
C1—C2—C3—C11	179.2 (3)	C66—N18—C60—O7	0.8 (5)
C10—N3—C4—O1	1.1 (5)	C66—N18—C60—C57	179.5 (3)
C10—N3—C4—C1	−179.7 (3)	N16—C57—C60—O7	23.1 (4)
N1—C1—C4—O1	−5.2 (4)	C58—C57—C60—O7	−158.9 (3)
C2—C1—C4—O1	170.5 (3)	N16—C57—C60—N18	−155.6 (3)
N1—C1—C4—N3	175.6 (3)	C58—C57—C60—N18	22.3 (4)
C2—C1—C4—N3	−8.6 (5)	C66—C61—C62—C63	0.4 (5)
C10—C5—C6—C7	−0.1 (5)	C61—C62—C63—C64	−1.2 (5)
C5—C6—C7—C8	0.0 (5)	C62—C63—C64—C65	0.9 (5)
C6—C7—C8—C9	0.3 (5)	C63—C64—C65—C66	0.2 (5)
C7—C8—C9—C10	−0.4 (5)	C62—C61—C66—C65	0.7 (5)
C8—C9—C10—C5	0.2 (5)	C62—C61—C66—N18	−177.9 (3)
C8—C9—C10—N3	−179.4 (3)	C64—C65—C66—C61	−1.0 (5)
C6—C5—C10—C9	0.0 (4)	C64—C65—C66—N18	177.7 (3)
C6—C5—C10—N3	179.7 (3)	C60—N18—C66—C61	−9.5 (5)
C4—N3—C10—C9	179.5 (3)	C60—N18—C66—C65	171.9 (3)
C4—N3—C10—C5	−0.2 (5)	C72—O9—C69—C70	−3.6 (5)
N5—N4—C12—C13	0.7 (3)	O9—C69—C70—C71	14.2 (5)
Cu1—N4—C12—C13	177.7 (2)	C69—C70—C71—C72	−18.6 (5)
N5—N4—C12—C15	176.7 (2)	C69—O9—C72—C71	−8.7 (5)
Cu1—N4—C12—C15	−6.2 (4)	C70—C71—C72—O9	16.9 (5)
N4—C12—C13—C14	−0.2 (3)	C76—O10—C73—C74	−42.4 (5)
C15—C12—C13—C14	−175.7 (3)	O10—C73—C74—C75	29.0 (5)
N4—N5—C14—C13	0.8 (3)	C73—C74—C75—C76	−3.9 (5)
B1—N5—C14—C13	179.0 (3)	C73—O10—C76—C75	39.3 (5)
N4—N5—C14—C22	−177.2 (3)	C74—C75—C76—O10	−21.1 (5)
B1—N5—C14—C22	0.9 (5)	C80—O11—C77—C78	−23.8 (5)
C12—C13—C14—N5	−0.4 (3)	O11—C77—C78—C79	24.0 (6)
C12—C13—C14—C22	177.4 (3)	C77—C78—C79—C80	−15.7 (6)
C21—N6—C15—O2	−5.1 (5)	C77—O11—C80—C79	14.4 (5)
C21—N6—C15—C12	175.4 (3)	C78—C79—C80—O11	1.3 (6)
N4—C12—C15—O2	−29.9 (4)	C84—O12—C81—C82	8.2 (5)
C13—C12—C15—O2	145.3 (3)	O12—C81—C82—C83	8.5 (6)
N4—C12—C15—N6	149.5 (3)	C81—C82—C83—C84	−20.4 (6)
C13—C12—C15—N6	−35.3 (4)	C81—O12—C84—C83	−21.5 (5)
C21—C16—C17—C18	−0.3 (5)	C82—C83—C84—O12	26.3 (6)
C16—C17—C18—C19	0.8 (5)	C88—O13—C85—C86	−16.7 (4)
C17—C18—C19—C20	−0.9 (6)	O13—C85—C86—C87	31.3 (4)
C18—C19—C20—C21	0.6 (6)	C85—C86—C87—C88	−34.1 (4)
C17—C16—C21—C20	0.0 (5)	C85—O13—C88—C87	−5.0 (4)
C17—C16—C21—N6	−178.4 (3)	C86—C87—C88—O13	25.0 (4)
C19—C20—C21—C16	−0.1 (5)	C92—O14—C89—C90	−33.7 (4)
C19—C20—C21—N6	178.4 (3)	O14—C89—C90—C91	22.3 (5)
C15—N6—C21—C16	−16.3 (5)	C89—C90—C91—C92	−3.4 (5)
C15—N6—C21—C20	165.2 (3)	C89—O14—C92—C91	31.1 (4)
N8—N7—C23—C24	−0.1 (3)	C90—C91—C92—O14	−16.6 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O9	0.82 (2)	2.21 (2)	3.011 (3)	165 (3)
N6—H6A···O10	0.81 (2)	2.27 (2)	3.043 (3)	159 (3)
N9—H9A···O11	0.82 (2)	2.19 (2)	2.986 (3)	167 (3)
N12—H12A···O12	0.81 (2)	2.22 (2)	3.001 (3)	162 (3)
N15—H15A···O13	0.83 (2)	2.14 (2)	2.947 (3)	165 (3)
N18—H18A···O14	0.81 (2)	2.19 (2)	2.987 (3)	165 (3)

(V) Carbonyl[tris(3-tert-butylaminocarbonyl-5-methylpyrazol-1-yl-κN²)borato]copper(I) tetrahydrofuran hemisolvate

Crystal data

[Cu(C27H43BN9O3)(CO)]·0.5C4H8O	F(000) = 2880
Mr = 680.12	Dx = 1.079 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9868 reflections
a = 15.1972 (11) Å	θ = 2.2–21.9°
b = 15.7870 (11) Å	µ = 0.56 mm^−1
c = 34.902 (3) Å	T = 200 K
V = 8373.6 (10) Å^3	Plate, colourless
Z = 8	0.43 × 0.15 × 0.12 mm

Data collection

Bruker APEXII area-detector diffractometer	19225 independent reflections
Radiation source: fine-focus sealed tube	14552 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.062
Detector resolution: 8.33 pixels mm^-1	θmax = 27.5°, θmin = 1.7°
ϕ and ω scans	h = −19→19
Absorption correction: multi-scan (APEX2; Bruker, 2007)	k = −20→20
Tmin = 0.793, Tmax = 0.935	l = −45→43
92865 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.135	w = 1/[σ^2(Fo^2) + (0.0782P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.002
19225 reflections	Δρmax = 0.55 e Å^−3
878 parameters	Δρmin = −0.34 e Å^−3
215 restraints	Absolute structure: Flack x determined using 5516 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.009 (4)

Special details

Experimental. Data collection is performed with four batch runs at ϕ = 0.00° (600 frames), at ϕ = 90.00° (600 frames), at ϕ = 180° (600 frames) and at ϕ = 270° (600 frames). Frame width = 0.30° in ω.

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. 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.

Data crystals were selected, sectioned if necessary, mounted on plastic mesh with viscous oil and cooled to 200 K. Diffraction data were collected on a Bruker APEXII DUO diffractometer, using Mo Kα radiation monochromated by graphite.

Data were corrected for absorption using multi-scan methods (Bruker, 2007), and the structure was solved using direct methods and refined using full-matrix least-squares based on F² with atomic scattering factors contained in the SHELX program suite (Sheldrick, 2008).

Systematic absences, equivalent reflections and unit-cell parameters were uniquely consistent with space group P2₁2₁2₁.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.60702 (4)	0.20389 (3)	0.60026 (2)	0.03630 (15)
Cu2	0.93150 (3)	0.40805 (3)	0.77043 (2)	0.02962 (13)
B1	0.7233 (3)	0.3572 (3)	0.61487 (16)	0.0353 (11)
H1	0.7611	0.4079	0.6198	0.042*
B2	0.8343 (3)	0.5114 (3)	0.83035 (15)	0.0296 (10)
H2	0.8012	0.5449	0.8500	0.036*
N1	0.5938 (3)	0.3198 (2)	0.57222 (11)	0.0390 (9)
N2	0.6590 (3)	0.3758 (2)	0.58146 (12)	0.0389 (9)
N3	0.6121 (2)	0.2698 (2)	0.65061 (11)	0.0333 (8)
N4	0.6700 (2)	0.3356 (2)	0.65113 (11)	0.0346 (8)
N5	0.7415 (2)	0.2062 (2)	0.59449 (11)	0.0349 (8)
N6	0.7815 (2)	0.2806 (2)	0.60387 (11)	0.0365 (8)
N7	0.4244 (3)	0.2609 (3)	0.54766 (13)	0.0556 (12)
H7	0.451 (4)	0.246 (4)	0.5676 (13)	0.067*
N8	0.5210 (3)	0.1696 (3)	0.73237 (13)	0.0433 (10)
H8	0.569 (3)	0.182 (3)	0.7443 (15)	0.052*
N9	0.8167 (3)	0.0401 (3)	0.53961 (12)	0.0455 (10)
H9	0.841 (3)	0.081 (3)	0.5286 (15)	0.055*
N10	0.9818 (2)	0.4398 (2)	0.82383 (10)	0.0289 (8)
N11	0.9247 (2)	0.4848 (2)	0.84656 (10)	0.0295 (8)
N12	1.2094 (2)	0.3966 (3)	0.84228 (12)	0.0392 (9)
H12	1.212 (3)	0.438 (3)	0.8577 (13)	0.047*
N13	0.8136 (2)	0.3704 (2)	0.79484 (10)	0.0288 (8)
N14	0.7810 (2)	0.4302 (2)	0.81947 (10)	0.0298 (8)
N15	0.8269 (2)	0.2188 (2)	0.74712 (11)	0.0331 (8)
H15	0.866 (3)	0.256 (3)	0.7499 (15)	0.040*
N16	0.8849 (2)	0.5304 (2)	0.76234 (10)	0.0287 (8)
N17	0.8485 (2)	0.5655 (2)	0.79399 (11)	0.0296 (8)
N18	0.9521 (3)	0.6425 (2)	0.67725 (12)	0.0412 (10)
H18	0.935 (4)	0.688 (2)	0.6877 (15)	0.049*
O1	0.4436 (3)	0.3435 (3)	0.49469 (11)	0.0639 (11)
O2	0.4669 (2)	0.1640 (3)	0.67126 (11)	0.0566 (10)
O3	0.7318 (3)	0.0203 (2)	0.59208 (10)	0.0516 (9)
O4	0.5199 (3)	0.0412 (3)	0.58947 (15)	0.0749 (14)
O5	1.1147 (2)	0.32505 (19)	0.80374 (10)	0.0401 (8)
O6	0.6958 (2)	0.17849 (19)	0.77292 (10)	0.0413 (8)
O7	0.9431 (2)	0.50127 (19)	0.68692 (10)	0.0441 (8)
O8	1.0568 (3)	0.3509 (2)	0.71195 (11)	0.0574 (10)
C1	0.5481 (3)	0.3549 (3)	0.54334 (14)	0.0433 (12)
C2	0.5844 (4)	0.4342 (4)	0.53402 (16)	0.0558 (15)
H2D	0.5644	0.4724	0.5149	0.067*
C3	0.6545 (4)	0.4451 (3)	0.55832 (16)	0.0497 (13)
C4	0.4680 (4)	0.3177 (3)	0.52629 (15)	0.0478 (13)
C5	0.3427 (4)	0.2157 (5)	0.5372 (2)	0.071 (2)
C6	0.2685 (5)	0.2779 (7)	0.5295 (3)	0.124 (4)
H6A	0.2608	0.3150	0.5517	0.186*
H6B	0.2138	0.2467	0.5247	0.186*
H6C	0.2829	0.3122	0.5069	0.186*
C7	0.3597 (7)	0.1614 (6)	0.5027 (3)	0.123 (4)
H7A	0.3730	0.1975	0.4807	0.184*
H7B	0.3073	0.1272	0.4972	0.184*
H7C	0.4097	0.1239	0.5078	0.184*
C8	0.3178 (5)	0.1618 (7)	0.5711 (3)	0.112 (3)
H8C	0.3676	0.1256	0.5781	0.167*
H8D	0.2672	0.1264	0.5644	0.167*
H8E	0.3025	0.1984	0.5928	0.167*
C9	0.7176 (5)	0.5172 (4)	0.5613 (2)	0.077 (2)
H9A	0.7045	0.5502	0.5844	0.116*
H9B	0.7117	0.5536	0.5387	0.116*
H9C	0.7778	0.4953	0.5628	0.116*
C10	0.5802 (3)	0.2625 (3)	0.68606 (14)	0.0361 (10)
C11	0.6173 (3)	0.3242 (3)	0.70967 (14)	0.0385 (11)
H11	0.6053	0.3333	0.7361	0.046*
C12	0.6743 (3)	0.3689 (3)	0.68719 (14)	0.0372 (10)
C13	0.5170 (3)	0.1929 (3)	0.69556 (15)	0.0393 (11)
C14	0.4696 (3)	0.1006 (4)	0.75021 (17)	0.0525 (14)
C15	0.4889 (4)	0.1068 (5)	0.79341 (19)	0.078 (2)
H15A	0.5518	0.0972	0.7979	0.117*
H15B	0.4546	0.0640	0.8071	0.117*
H15C	0.4727	0.1633	0.8027	0.117*
C16	0.4994 (5)	0.0163 (4)	0.7336 (3)	0.085 (2)
H16A	0.4903	0.0164	0.7058	0.127*
H16B	0.4652	−0.0297	0.7452	0.127*
H16C	0.5620	0.0078	0.7392	0.127*
C17	0.3712 (3)	0.1170 (5)	0.7433 (2)	0.075 (2)
H17A	0.3554	0.1728	0.7535	0.112*
H17B	0.3364	0.0732	0.7561	0.112*
H17C	0.3592	0.1156	0.7157	0.112*
C18	0.7353 (4)	0.4406 (3)	0.69723 (16)	0.0502 (13)
H18A	0.7963	0.4231	0.6928	0.075*
H18B	0.7276	0.4557	0.7243	0.075*
H18C	0.7217	0.4898	0.6812	0.075*
C19	0.8054 (3)	0.1522 (3)	0.58530 (13)	0.0329 (10)
C20	0.8878 (3)	0.1903 (3)	0.58910 (14)	0.0424 (11)
H20	0.9436	0.1655	0.5844	0.051*
C21	0.8707 (3)	0.2723 (3)	0.60129 (15)	0.0402 (11)
C22	0.7807 (3)	0.0646 (3)	0.57259 (14)	0.0375 (11)
C23	0.7928 (4)	−0.0361 (4)	0.51750 (17)	0.0596 (15)
C24	0.8464 (8)	−0.0351 (6)	0.4811 (2)	0.123 (4)
H24A	0.8345	0.0173	0.4669	0.184*
H24B	0.8305	−0.0839	0.4652	0.184*
H24C	0.9092	−0.0379	0.4875	0.184*
C25	0.8135 (5)	−0.1172 (4)	0.5399 (2)	0.080 (2)
H25A	0.8770	−0.1278	0.5392	0.120*
H25B	0.7824	−0.1650	0.5282	0.120*
H25C	0.7943	−0.1105	0.5665	0.120*
C26	0.6979 (6)	−0.0320 (6)	0.5070 (3)	0.106 (3)
H26A	0.6620	−0.0352	0.5303	0.159*
H26B	0.6833	−0.0796	0.4902	0.159*
H26C	0.6859	0.0214	0.4937	0.159*
C27	0.9331 (4)	0.3432 (3)	0.61029 (19)	0.0583 (15)
H27A	0.9252	0.3889	0.5916	0.087*
H27B	0.9937	0.3223	0.6091	0.087*
H27C	0.9210	0.3648	0.6361	0.087*
C28	0.5512 (3)	0.1050 (3)	0.59284 (15)	0.0463 (12)
C29	1.0559 (3)	0.4305 (3)	0.84436 (13)	0.0308 (9)
C30	1.0465 (3)	0.4693 (3)	0.88014 (13)	0.0343 (10)
H30	1.0891	0.4722	0.9000	0.041*
C31	0.9626 (3)	0.5026 (3)	0.88058 (13)	0.0336 (10)
C32	1.1299 (3)	0.3799 (3)	0.82827 (13)	0.0327 (10)
C33	1.2912 (3)	0.3508 (3)	0.83097 (17)	0.0469 (13)
C34	1.3664 (3)	0.3932 (4)	0.8535 (2)	0.075 (2)
H34A	1.3686	0.4536	0.8472	0.112*
H34B	1.4225	0.3665	0.8466	0.112*
H34C	1.3561	0.3863	0.8811	0.112*
C35	1.3067 (4)	0.3599 (4)	0.78789 (17)	0.0590 (15)
H35A	1.2577	0.3340	0.7739	0.089*
H35B	1.3617	0.3313	0.7809	0.089*
H35C	1.3108	0.4200	0.7812	0.089*
C36	1.2843 (4)	0.2584 (4)	0.8423 (2)	0.0619 (16)
H36A	1.2732	0.2541	0.8699	0.093*
H36B	1.3396	0.2294	0.8361	0.093*
H36C	1.2358	0.2318	0.8282	0.093*
C37	0.9153 (3)	0.5489 (4)	0.91212 (15)	0.0466 (13)
H37A	0.8981	0.6053	0.9031	0.070*
H37B	0.9543	0.5546	0.9343	0.070*
H37C	0.8626	0.5171	0.9195	0.070*
C38	0.7521 (3)	0.3095 (3)	0.79327 (13)	0.0310 (9)
C39	0.6808 (3)	0.3298 (3)	0.81634 (14)	0.0401 (11)
H39	0.6290	0.2972	0.8201	0.048*
C40	0.7006 (3)	0.4067 (3)	0.83269 (13)	0.0350 (10)
C41	0.7568 (3)	0.2294 (3)	0.76967 (13)	0.0324 (9)
C42	0.8430 (3)	0.1440 (3)	0.72189 (13)	0.0351 (10)
C43	0.8546 (4)	0.0650 (3)	0.74587 (16)	0.0470 (12)
H43A	0.9010	0.0744	0.7649	0.070*
H43B	0.8710	0.0175	0.7293	0.070*
H43C	0.7992	0.0519	0.7590	0.070*
C44	0.7673 (3)	0.1341 (3)	0.69324 (15)	0.0443 (12)
H44A	0.7129	0.1210	0.7071	0.067*
H44B	0.7809	0.0881	0.6754	0.067*
H44C	0.7598	0.1871	0.6789	0.067*
C45	0.9277 (3)	0.1632 (3)	0.70024 (15)	0.0436 (11)
H45A	0.9195	0.2140	0.6845	0.065*
H45B	0.9426	0.1151	0.6837	0.065*
H45C	0.9755	0.1728	0.7186	0.065*
C46	0.6466 (3)	0.4587 (3)	0.86000 (16)	0.0501 (13)
H46A	0.6795	0.4671	0.8838	0.075*
H46B	0.5914	0.4292	0.8656	0.075*
H46C	0.6337	0.5139	0.8484	0.075*
C47	0.8907 (3)	0.5925 (3)	0.73616 (12)	0.0288 (8)
C48	0.8575 (3)	0.6683 (3)	0.75116 (14)	0.0338 (10)
H48	0.8537	0.7216	0.7386	0.041*
C49	0.8315 (3)	0.6493 (3)	0.78796 (13)	0.0306 (9)
C50	0.9307 (3)	0.5740 (3)	0.69787 (12)	0.0322 (9)
C51	0.9928 (4)	0.6395 (3)	0.63866 (16)	0.0555 (15)
C52	1.0075 (7)	0.7324 (4)	0.6259 (2)	0.099 (3)
H52A	0.9532	0.7648	0.6296	0.148*
H52B	1.0240	0.7335	0.5987	0.148*
H52C	1.0548	0.7576	0.6412	0.148*
C53	0.9302 (6)	0.5969 (4)	0.61045 (18)	0.084 (2)
H53A	0.9230	0.5372	0.6174	0.126*
H53B	0.9545	0.6009	0.5845	0.126*
H53C	0.8729	0.6253	0.6113	0.126*
C54	1.0812 (5)	0.5925 (5)	0.6406 (2)	0.092 (2)
H54A	1.1177	0.6174	0.6608	0.138*
H54B	1.1116	0.5977	0.6159	0.138*
H54C	1.0708	0.5326	0.6462	0.138*
C55	0.7925 (3)	0.7058 (3)	0.81796 (15)	0.0447 (12)
H55A	0.7337	0.6852	0.8248	0.067*
H55B	0.7881	0.7637	0.8080	0.067*
H55C	0.8302	0.7055	0.8407	0.067*
C56	1.0055 (3)	0.3682 (3)	0.73386 (14)	0.0359 (10)
O100	0.3756 (9)	0.4005 (10)	0.6745 (4)	0.156 (4)	0.587 (7)
C101	0.3907 (15)	0.3637 (14)	0.6395 (5)	0.156 (5)	0.587 (7)
H10A	0.3552	0.3116	0.6364	0.187*	0.587 (7)
H10B	0.4537	0.3493	0.6364	0.187*	0.587 (7)
C102	0.3616 (14)	0.4339 (17)	0.6095 (5)	0.165 (6)	0.587 (7)
H10C	0.3613	0.4138	0.5827	0.198*	0.587 (7)
H10D	0.3947	0.4877	0.6119	0.198*	0.587 (7)
C103	0.2657 (11)	0.4368 (15)	0.6288 (5)	0.146 (5)	0.587 (7)
H10E	0.2338	0.3823	0.6270	0.175*	0.587 (7)
H10F	0.2287	0.4838	0.6191	0.175*	0.587 (7)
C104	0.3058 (13)	0.4546 (14)	0.6706 (5)	0.137 (5)	0.587 (7)
H10G	0.3255	0.5142	0.6728	0.165*	0.587 (7)
H10H	0.2611	0.4435	0.6906	0.165*	0.587 (7)
O200	0.4055 (12)	0.5007 (14)	0.6281 (6)	0.156 (4)	0.413 (7)
C201	0.3175 (15)	0.5163 (15)	0.6330 (9)	0.156 (5)	0.413 (7)
H20A	0.2868	0.5192	0.6080	0.187*	0.413 (7)
H20B	0.3080	0.5701	0.6470	0.187*	0.413 (7)
C202	0.2838 (17)	0.4356 (19)	0.6580 (9)	0.165 (6)	0.413 (7)
H20C	0.2194	0.4338	0.6623	0.198*	0.413 (7)
H20D	0.3169	0.4259	0.6820	0.198*	0.413 (7)
C203	0.3189 (15)	0.3781 (14)	0.6204 (9)	0.146 (5)	0.413 (7)
H20E	0.2983	0.3982	0.5951	0.175*	0.413 (7)
H20F	0.3123	0.3160	0.6233	0.175*	0.413 (7)
C204	0.4199 (13)	0.4186 (16)	0.6351 (8)	0.137 (5)	0.413 (7)
H20G	0.4311	0.4077	0.6626	0.165*	0.413 (7)
H20H	0.4691	0.3960	0.6196	0.165*	0.413 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0391 (3)	0.0342 (3)	0.0356 (3)	−0.0053 (2)	−0.0045 (2)	0.0011 (2)
Cu2	0.0300 (2)	0.0263 (2)	0.0326 (3)	0.0011 (2)	0.0034 (2)	−0.0026 (2)
B1	0.038 (3)	0.027 (2)	0.041 (3)	−0.004 (2)	−0.005 (2)	0.002 (2)
B2	0.027 (2)	0.028 (2)	0.034 (3)	0.0034 (19)	0.003 (2)	−0.003 (2)
N1	0.042 (2)	0.041 (2)	0.035 (2)	−0.0036 (17)	−0.0044 (17)	0.0064 (17)
N2	0.040 (2)	0.035 (2)	0.042 (2)	−0.0049 (17)	−0.0036 (17)	0.0054 (17)
N3	0.0323 (18)	0.0315 (19)	0.036 (2)	−0.0019 (16)	−0.0049 (16)	−0.0002 (15)
N4	0.0353 (19)	0.0311 (19)	0.037 (2)	0.0006 (16)	−0.0067 (16)	−0.0039 (16)
N5	0.0368 (19)	0.0318 (18)	0.036 (2)	−0.0041 (17)	0.0000 (16)	0.0025 (17)
N6	0.038 (2)	0.033 (2)	0.039 (2)	−0.0044 (16)	−0.0015 (17)	0.0001 (17)
N7	0.049 (3)	0.071 (3)	0.047 (3)	−0.009 (2)	−0.011 (2)	0.020 (2)
N8	0.029 (2)	0.056 (3)	0.045 (3)	−0.0013 (18)	0.0014 (18)	0.008 (2)
N9	0.063 (3)	0.039 (2)	0.035 (2)	−0.006 (2)	0.007 (2)	−0.0023 (18)
N10	0.0300 (18)	0.0222 (16)	0.034 (2)	0.0024 (14)	0.0009 (15)	−0.0023 (15)
N11	0.0305 (18)	0.0278 (17)	0.0303 (19)	0.0004 (15)	0.0064 (15)	−0.0017 (14)
N12	0.0313 (19)	0.037 (2)	0.049 (2)	0.0036 (17)	−0.0020 (17)	−0.0145 (19)
N13	0.0306 (18)	0.0257 (17)	0.030 (2)	0.0007 (14)	0.0015 (15)	−0.0022 (15)
N14	0.0261 (17)	0.0292 (19)	0.034 (2)	0.0004 (14)	0.0027 (15)	−0.0032 (15)
N15	0.0288 (18)	0.030 (2)	0.040 (2)	−0.0023 (15)	−0.0002 (16)	−0.0045 (16)
N16	0.0305 (18)	0.0252 (17)	0.030 (2)	0.0006 (15)	0.0020 (15)	−0.0010 (14)
N17	0.0278 (17)	0.0251 (17)	0.036 (2)	0.0005 (14)	0.0005 (15)	−0.0006 (15)
N18	0.058 (3)	0.028 (2)	0.038 (2)	−0.0035 (18)	0.0120 (19)	0.0010 (17)
O1	0.072 (3)	0.072 (3)	0.048 (2)	−0.012 (2)	−0.026 (2)	0.021 (2)
O2	0.046 (2)	0.069 (2)	0.055 (2)	−0.0141 (19)	−0.0062 (18)	0.000 (2)
O3	0.064 (2)	0.0392 (19)	0.051 (2)	−0.0114 (17)	0.0167 (18)	0.0011 (17)
O4	0.070 (3)	0.045 (2)	0.111 (4)	−0.022 (2)	−0.004 (3)	−0.006 (2)
O5	0.0363 (17)	0.0332 (16)	0.051 (2)	0.0016 (14)	−0.0033 (15)	−0.0110 (15)
O6	0.0381 (17)	0.0366 (17)	0.049 (2)	−0.0098 (14)	0.0032 (15)	−0.0041 (16)
O7	0.062 (2)	0.0287 (16)	0.0417 (19)	0.0040 (16)	0.0084 (17)	−0.0005 (14)
O8	0.061 (2)	0.056 (2)	0.056 (2)	0.017 (2)	0.027 (2)	0.0041 (18)
C1	0.046 (3)	0.046 (3)	0.037 (3)	−0.001 (2)	−0.005 (2)	0.008 (2)
C2	0.067 (4)	0.052 (3)	0.048 (3)	−0.003 (3)	−0.013 (3)	0.019 (3)
C3	0.056 (3)	0.040 (3)	0.053 (3)	−0.005 (2)	−0.007 (3)	0.016 (2)
C4	0.051 (3)	0.053 (3)	0.040 (3)	0.000 (2)	−0.009 (2)	0.009 (2)
C5	0.056 (4)	0.075 (4)	0.084 (5)	−0.016 (3)	−0.022 (3)	0.029 (4)
C6	0.051 (4)	0.132 (8)	0.189 (10)	−0.024 (5)	−0.035 (5)	0.066 (7)
C7	0.157 (9)	0.112 (7)	0.099 (7)	−0.079 (7)	−0.025 (6)	0.011 (6)
C8	0.081 (5)	0.145 (8)	0.109 (7)	−0.040 (5)	−0.009 (5)	0.074 (6)
C9	0.086 (5)	0.054 (4)	0.091 (5)	−0.024 (3)	−0.028 (4)	0.029 (4)
C10	0.030 (2)	0.039 (2)	0.039 (3)	0.0047 (19)	−0.0023 (19)	0.000 (2)
C11	0.037 (2)	0.045 (3)	0.034 (3)	0.009 (2)	−0.003 (2)	−0.002 (2)
C12	0.039 (2)	0.033 (2)	0.040 (3)	0.009 (2)	−0.009 (2)	−0.005 (2)
C13	0.030 (2)	0.045 (3)	0.043 (3)	0.004 (2)	0.004 (2)	0.000 (2)
C14	0.033 (2)	0.060 (3)	0.064 (4)	0.001 (2)	0.008 (2)	0.015 (3)
C15	0.055 (4)	0.108 (6)	0.070 (5)	−0.001 (4)	0.013 (3)	0.032 (4)
C16	0.080 (5)	0.054 (4)	0.121 (7)	0.000 (3)	0.002 (5)	0.018 (4)
C17	0.031 (3)	0.094 (5)	0.099 (5)	0.000 (3)	0.009 (3)	0.030 (4)
C18	0.059 (3)	0.042 (3)	0.050 (3)	−0.002 (2)	−0.007 (3)	−0.010 (2)
C19	0.039 (2)	0.032 (2)	0.028 (2)	0.0008 (19)	0.0034 (18)	0.0041 (18)
C20	0.037 (2)	0.043 (3)	0.047 (3)	0.004 (2)	0.003 (2)	0.000 (2)
C21	0.038 (2)	0.043 (3)	0.039 (3)	−0.0029 (19)	0.003 (2)	0.002 (2)
C22	0.038 (2)	0.035 (2)	0.039 (3)	0.000 (2)	0.001 (2)	0.005 (2)
C23	0.072 (4)	0.057 (4)	0.050 (3)	−0.007 (3)	0.002 (3)	−0.017 (3)
C24	0.199 (11)	0.102 (6)	0.066 (5)	−0.027 (7)	0.046 (6)	−0.044 (5)
C25	0.104 (6)	0.048 (4)	0.088 (5)	0.008 (4)	−0.012 (4)	−0.019 (3)
C26	0.104 (7)	0.102 (6)	0.112 (7)	−0.009 (5)	−0.047 (5)	−0.029 (5)
C27	0.043 (3)	0.048 (3)	0.084 (4)	−0.006 (3)	−0.002 (3)	−0.009 (3)
C28	0.045 (3)	0.044 (3)	0.050 (3)	−0.005 (2)	−0.001 (2)	0.004 (2)
C29	0.030 (2)	0.025 (2)	0.038 (2)	−0.0020 (16)	0.0019 (18)	−0.0017 (17)
C30	0.032 (2)	0.037 (2)	0.034 (2)	−0.0002 (18)	−0.0033 (18)	−0.006 (2)
C31	0.032 (2)	0.035 (2)	0.034 (2)	−0.0052 (18)	−0.0010 (19)	−0.0032 (19)
C32	0.034 (2)	0.023 (2)	0.041 (3)	0.0013 (17)	−0.0002 (19)	−0.0011 (18)
C33	0.031 (2)	0.046 (3)	0.064 (4)	0.008 (2)	0.000 (2)	−0.019 (3)
C34	0.030 (3)	0.089 (5)	0.105 (5)	0.008 (3)	−0.010 (3)	−0.048 (4)
C35	0.049 (3)	0.060 (4)	0.068 (4)	−0.006 (3)	0.016 (3)	−0.015 (3)
C36	0.050 (3)	0.060 (4)	0.076 (4)	0.022 (3)	−0.007 (3)	−0.005 (3)
C37	0.039 (3)	0.059 (3)	0.042 (3)	−0.001 (2)	0.003 (2)	−0.013 (2)
C38	0.031 (2)	0.030 (2)	0.033 (2)	−0.0034 (18)	−0.0004 (18)	0.0002 (18)
C39	0.035 (2)	0.040 (3)	0.046 (3)	−0.010 (2)	0.007 (2)	−0.002 (2)
C40	0.032 (2)	0.039 (2)	0.033 (2)	0.000 (2)	0.0054 (18)	−0.003 (2)
C41	0.037 (2)	0.030 (2)	0.030 (2)	0.0003 (18)	−0.009 (2)	0.0023 (19)
C42	0.038 (2)	0.029 (2)	0.039 (3)	0.0026 (18)	−0.0042 (19)	−0.0042 (19)
C43	0.051 (3)	0.038 (3)	0.052 (3)	0.009 (2)	0.000 (2)	0.000 (2)
C44	0.044 (3)	0.044 (3)	0.045 (3)	0.006 (2)	−0.012 (2)	−0.011 (2)
C45	0.041 (3)	0.045 (3)	0.045 (3)	0.006 (2)	0.005 (2)	−0.006 (2)
C46	0.042 (3)	0.051 (3)	0.057 (3)	−0.003 (2)	0.022 (3)	−0.012 (3)
C47	0.0255 (18)	0.0249 (19)	0.036 (2)	0.0011 (17)	−0.0025 (17)	0.0021 (18)
C48	0.028 (2)	0.029 (2)	0.045 (3)	−0.0002 (17)	−0.0020 (19)	0.003 (2)
C49	0.024 (2)	0.027 (2)	0.040 (3)	0.0018 (17)	0.0022 (18)	−0.0004 (18)
C50	0.032 (2)	0.029 (2)	0.035 (2)	0.0004 (18)	−0.0019 (19)	0.0026 (17)
C51	0.090 (4)	0.038 (3)	0.039 (3)	0.001 (3)	0.027 (3)	0.000 (2)
C52	0.177 (9)	0.050 (4)	0.070 (5)	−0.011 (4)	0.067 (5)	0.005 (3)
C53	0.140 (7)	0.065 (4)	0.047 (4)	−0.003 (5)	0.003 (4)	−0.002 (3)
C54	0.084 (5)	0.108 (6)	0.083 (5)	0.023 (5)	0.041 (4)	0.011 (5)
C55	0.052 (3)	0.031 (2)	0.051 (3)	0.009 (2)	0.009 (2)	−0.004 (2)
C56	0.038 (2)	0.030 (2)	0.040 (3)	0.0012 (19)	0.001 (2)	0.000 (2)
O100	0.123 (7)	0.193 (10)	0.153 (8)	0.021 (7)	−0.017 (6)	−0.046 (7)
C101	0.126 (10)	0.183 (12)	0.158 (11)	0.054 (9)	−0.005 (10)	−0.016 (9)
C102	0.149 (11)	0.200 (14)	0.146 (10)	0.036 (10)	0.010 (9)	−0.010 (10)
C103	0.121 (9)	0.169 (11)	0.148 (10)	0.052 (7)	−0.032 (8)	−0.027 (10)
C104	0.115 (9)	0.162 (11)	0.135 (10)	0.023 (8)	−0.004 (7)	−0.049 (9)
O200	0.123 (7)	0.193 (10)	0.153 (8)	0.021 (7)	−0.017 (6)	−0.046 (7)
C201	0.126 (10)	0.183 (12)	0.158 (11)	0.054 (9)	−0.005 (10)	−0.016 (9)
C202	0.149 (11)	0.200 (14)	0.146 (10)	0.036 (10)	0.010 (9)	−0.010 (10)
C203	0.121 (9)	0.169 (11)	0.148 (10)	0.052 (7)	−0.032 (8)	−0.027 (10)
C204	0.115 (9)	0.162 (11)	0.135 (10)	0.023 (8)	−0.004 (7)	−0.049 (9)

Geometric parameters (Å, º)

Cu1—C28	1.795 (5)	C20—H20	0.9500
Cu1—N3	2.044 (4)	C21—C27	1.500 (7)
Cu1—N5	2.055 (4)	C23—C26	1.489 (10)
Cu1—N1	2.085 (4)	C23—C24	1.510 (10)
Cu2—C56	1.814 (5)	C23—C25	1.532 (9)
Cu2—N13	2.071 (3)	C24—H24A	0.9800
Cu2—N10	2.076 (4)	C24—H24B	0.9800
Cu2—N16	2.077 (3)	C24—H24C	0.9800
B1—N4	1.541 (7)	C25—H25A	0.9800
B1—N6	1.548 (6)	C25—H25B	0.9800
B1—N2	1.549 (7)	C25—H25C	0.9800
B1—H1	1.0000	C26—H26A	0.9800
B2—N11	1.544 (6)	C26—H26B	0.9800
B2—N17	1.545 (6)	C26—H26C	0.9800
B2—N14	1.562 (6)	C27—H27A	0.9800
B2—H2	1.0000	C27—H27B	0.9800
N1—C1	1.343 (6)	C27—H27C	0.9800
N1—N2	1.366 (5)	C29—C30	1.398 (6)
N2—C3	1.361 (6)	C29—C32	1.490 (6)
N3—C10	1.334 (6)	C30—C31	1.379 (6)
N3—N4	1.361 (5)	C30—H30	0.9500
N4—C12	1.366 (6)	C31—C37	1.505 (7)
N5—C19	1.331 (6)	C33—C36	1.516 (8)
N5—N6	1.363 (5)	C33—C35	1.529 (8)
N6—C21	1.364 (6)	C33—C34	1.541 (7)
N7—C4	1.341 (7)	C34—H34A	0.9800
N7—C5	1.478 (8)	C34—H34B	0.9800
N7—H7	0.84 (3)	C34—H34C	0.9800
N8—C13	1.338 (7)	C35—H35A	0.9800
N8—C14	1.478 (7)	C35—H35B	0.9800
N8—H8	0.86 (3)	C35—H35C	0.9800
N9—C22	1.332 (6)	C36—H36A	0.9800
N9—C23	1.475 (7)	C36—H36B	0.9800
N9—H9	0.84 (3)	C36—H36C	0.9800
N10—C29	1.342 (6)	C37—H37A	0.9800
N10—N11	1.374 (5)	C37—H37B	0.9800
N11—C31	1.349 (6)	C37—H37C	0.9800
N12—C32	1.330 (6)	C38—C39	1.387 (6)
N12—C33	1.491 (6)	C38—C41	1.510 (6)
N12—H12	0.85 (3)	C39—C40	1.375 (7)
N13—C38	1.342 (5)	C39—H39	0.9500
N13—N14	1.370 (5)	C40—C46	1.503 (6)
N14—C40	1.358 (5)	C42—C43	1.512 (7)
N15—C41	1.334 (6)	C42—C45	1.523 (7)
N15—C42	1.493 (6)	C42—C44	1.531 (6)
N15—H15	0.84 (3)	C43—H43A	0.9800
N16—C47	1.343 (5)	C43—H43B	0.9800
N16—N17	1.354 (5)	C43—H43C	0.9800
N17—C49	1.363 (5)	C44—H44A	0.9800
N18—C50	1.340 (6)	C44—H44B	0.9800
N18—C51	1.483 (6)	C44—H44C	0.9800
N18—H18	0.85 (3)	C45—H45A	0.9800
O1—C4	1.233 (6)	C45—H45B	0.9800
O2—C13	1.228 (6)	C45—H45C	0.9800
O3—C22	1.227 (6)	C46—H46A	0.9800
O4—C28	1.120 (6)	C46—H46B	0.9800
O5—C32	1.239 (5)	C46—H46C	0.9800
O6—C41	1.232 (5)	C47—C48	1.400 (6)
O7—C50	1.225 (5)	C47—C50	1.497 (6)
O8—C56	1.125 (5)	C48—C49	1.377 (7)
C1—C2	1.407 (7)	C48—H48	0.9500
C1—C4	1.476 (7)	C49—C55	1.498 (6)
C2—C3	1.373 (8)	C51—C53	1.526 (10)
C2—H2D	0.9500	C51—C54	1.537 (9)
C3—C9	1.492 (8)	C51—C52	1.549 (8)
C5—C7	1.500 (12)	C52—H52A	0.9800
C5—C8	1.504 (10)	C52—H52B	0.9800
C5—C6	1.521 (11)	C52—H52C	0.9800
C6—H6A	0.9800	C53—H53A	0.9800
C6—H6B	0.9800	C53—H53B	0.9800
C6—H6C	0.9800	C53—H53C	0.9800
C7—H7A	0.9800	C54—H54A	0.9800
C7—H7B	0.9800	C54—H54B	0.9800
C7—H7C	0.9800	C54—H54C	0.9800
C8—H8C	0.9800	C55—H55A	0.9800
C8—H8D	0.9800	C55—H55B	0.9800
C8—H8E	0.9800	C55—H55C	0.9800
C9—H9A	0.9800	O100—C104	1.369 (16)
C9—H9B	0.9800	O100—C101	1.374 (17)
C9—H9C	0.9800	C101—C102	1.588 (19)
C10—C11	1.395 (7)	C101—H10A	0.9900
C10—C13	1.496 (7)	C101—H10B	0.9900
C11—C12	1.365 (7)	C102—C103	1.605 (19)
C11—H11	0.9500	C102—H10C	0.9900
C12—C18	1.505 (7)	C102—H10D	0.9900
C14—C16	1.521 (9)	C103—C104	1.607 (17)
C14—C17	1.537 (7)	C103—H10E	0.9900
C14—C15	1.539 (9)	C103—H10F	0.9900
C15—H15A	0.9800	C104—H10G	0.9900
C15—H15B	0.9800	C104—H10H	0.9900
C15—H15C	0.9800	O200—C204	1.337 (19)
C16—H16A	0.9800	O200—C201	1.369 (18)
C16—H16B	0.9800	C201—C202	1.63 (2)
C16—H16C	0.9800	C201—H20A	0.9900
C17—H17A	0.9800	C201—H20B	0.9900
C17—H17B	0.9800	C202—C203	1.68 (2)
C17—H17C	0.9800	C202—H20C	0.9900
C18—H18A	0.9800	C202—H20D	0.9900
C18—H18B	0.9800	C203—C204	1.74 (2)
C18—H18C	0.9800	C203—H20E	0.9900
C19—C20	1.395 (7)	C203—H20F	0.9900
C19—C22	1.499 (7)	C204—H20G	0.9900
C20—C21	1.387 (7)	C204—H20H	0.9900
C28—Cu1—N3	125.8 (2)	H25B—C25—H25C	109.5
C28—Cu1—N5	118.1 (2)	C23—C26—H26A	109.5
N3—Cu1—N5	92.15 (15)	C23—C26—H26B	109.5
C28—Cu1—N1	130.5 (2)	H26A—C26—H26B	109.5
N3—Cu1—N1	87.74 (15)	C23—C26—H26C	109.5
N5—Cu1—N1	91.99 (15)	H26A—C26—H26C	109.5
C56—Cu2—N13	136.60 (17)	H26B—C26—H26C	109.5
C56—Cu2—N10	119.14 (18)	C21—C27—H27A	109.5
N13—Cu2—N10	91.07 (14)	C21—C27—H27B	109.5
C56—Cu2—N16	116.02 (17)	H27A—C27—H27B	109.5
N13—Cu2—N16	91.58 (14)	C21—C27—H27C	109.5
N10—Cu2—N16	91.31 (14)	H27A—C27—H27C	109.5
N4—B1—N6	109.3 (4)	H27B—C27—H27C	109.5
N4—B1—N2	109.2 (4)	O4—C28—Cu1	176.1 (5)
N6—B1—N2	108.8 (4)	N10—C29—C30	110.1 (4)
N4—B1—H1	109.8	N10—C29—C32	119.4 (4)
N6—B1—H1	109.8	C30—C29—C32	130.5 (4)
N2—B1—H1	109.8	C31—C30—C29	105.7 (4)
N11—B2—N17	109.1 (3)	C31—C30—H30	127.1
N11—B2—N14	109.1 (3)	C29—C30—H30	127.1
N17—B2—N14	109.0 (4)	N11—C31—C30	107.8 (4)
N11—B2—H2	109.8	N11—C31—C37	122.7 (4)
N17—B2—H2	109.8	C30—C31—C37	129.4 (4)
N14—B2—H2	109.8	O5—C32—N12	124.2 (4)
C1—N1—N2	106.6 (4)	O5—C32—C29	119.7 (4)
C1—N1—Cu1	139.8 (3)	N12—C32—C29	116.1 (4)
N2—N1—Cu1	112.8 (3)	N12—C33—C36	110.0 (4)
C3—N2—N1	110.1 (4)	N12—C33—C35	110.1 (4)
C3—N2—B1	129.0 (4)	C36—C33—C35	110.9 (5)
N1—N2—B1	120.8 (4)	N12—C33—C34	105.8 (4)
C10—N3—N4	106.8 (4)	C36—C33—C34	109.6 (5)
C10—N3—Cu1	137.7 (3)	C35—C33—C34	110.3 (5)
N4—N3—Cu1	115.1 (3)	C33—C34—H34A	109.5
N3—N4—C12	109.7 (4)	C33—C34—H34B	109.5
N3—N4—B1	119.9 (4)	H34A—C34—H34B	109.5
C12—N4—B1	130.3 (4)	C33—C34—H34C	109.5
C19—N5—N6	106.5 (4)	H34A—C34—H34C	109.5
C19—N5—Cu1	137.6 (3)	H34B—C34—H34C	109.5
N6—N5—Cu1	115.8 (3)	C33—C35—H35A	109.5
N5—N6—C21	110.2 (4)	C33—C35—H35B	109.5
N5—N6—B1	118.6 (3)	H35A—C35—H35B	109.5
C21—N6—B1	131.2 (4)	C33—C35—H35C	109.5
C4—N7—C5	126.9 (5)	H35A—C35—H35C	109.5
C4—N7—H7	114 (4)	H35B—C35—H35C	109.5
C5—N7—H7	119 (4)	C33—C36—H36A	109.5
C13—N8—C14	125.7 (5)	C33—C36—H36B	109.5
C13—N8—H8	116 (4)	H36A—C36—H36B	109.5
C14—N8—H8	114 (4)	C33—C36—H36C	109.5
C22—N9—C23	126.0 (5)	H36A—C36—H36C	109.5
C22—N9—H9	111 (4)	H36B—C36—H36C	109.5
C23—N9—H9	120 (4)	C31—C37—H37A	109.5
C29—N10—N11	106.2 (3)	C31—C37—H37B	109.5
C29—N10—Cu2	139.6 (3)	H37A—C37—H37B	109.5
N11—N10—Cu2	114.2 (3)	C31—C37—H37C	109.5
C31—N11—N10	110.2 (4)	H37A—C37—H37C	109.5
C31—N11—B2	130.2 (4)	H37B—C37—H37C	109.5
N10—N11—B2	119.4 (3)	N13—C38—C39	110.7 (4)
C32—N12—C33	124.3 (4)	N13—C38—C41	126.1 (4)
C32—N12—H12	115 (4)	C39—C38—C41	123.2 (4)
C33—N12—H12	121 (4)	C40—C39—C38	105.9 (4)
C38—N13—N14	105.5 (3)	C40—C39—H39	127.0
C38—N13—Cu2	142.3 (3)	C38—C39—H39	127.0
N14—N13—Cu2	111.9 (2)	N14—C40—C39	107.3 (4)
C40—N14—N13	110.5 (3)	N14—C40—C46	123.9 (4)
C40—N14—B2	127.5 (4)	C39—C40—C46	128.8 (4)
N13—N14—B2	122.0 (3)	O6—C41—N15	124.9 (4)
C41—N15—C42	125.3 (4)	O6—C41—C38	117.4 (4)
C41—N15—H15	114 (4)	N15—C41—C38	117.7 (4)
C42—N15—H15	120 (4)	N15—C42—C43	110.2 (4)
C47—N16—N17	106.4 (3)	N15—C42—C45	105.9 (4)
C47—N16—Cu2	138.5 (3)	C43—C42—C45	109.9 (4)
N17—N16—Cu2	114.2 (2)	N15—C42—C44	110.0 (4)
N16—N17—C49	110.4 (4)	C43—C42—C44	111.4 (4)
N16—N17—B2	120.0 (3)	C45—C42—C44	109.3 (4)
C49—N17—B2	129.6 (4)	C42—C43—H43A	109.5
C50—N18—C51	124.3 (4)	C42—C43—H43B	109.5
C50—N18—H18	112 (4)	H43A—C43—H43B	109.5
C51—N18—H18	123 (4)	C42—C43—H43C	109.5
N1—C1—C2	109.8 (4)	H43A—C43—H43C	109.5
N1—C1—C4	124.4 (4)	H43B—C43—H43C	109.5
C2—C1—C4	125.7 (5)	C42—C44—H44A	109.5
C3—C2—C1	105.8 (5)	C42—C44—H44B	109.5
C3—C2—H2D	127.1	H44A—C44—H44B	109.5
C1—C2—H2D	127.1	C42—C44—H44C	109.5
N2—C3—C2	107.7 (5)	H44A—C44—H44C	109.5
N2—C3—C9	122.7 (5)	H44B—C44—H44C	109.5
C2—C3—C9	129.5 (5)	C42—C45—H45A	109.5
O1—C4—N7	124.7 (5)	C42—C45—H45B	109.5
O1—C4—C1	118.5 (5)	H45A—C45—H45B	109.5
N7—C4—C1	116.7 (5)	C42—C45—H45C	109.5
N7—C5—C7	109.3 (6)	H45A—C45—H45C	109.5
N7—C5—C8	106.9 (6)	H45B—C45—H45C	109.5
C7—C5—C8	110.5 (7)	C40—C46—H46A	109.5
N7—C5—C6	110.8 (6)	C40—C46—H46B	109.5
C7—C5—C6	110.7 (8)	H46A—C46—H46B	109.5
C8—C5—C6	108.6 (7)	C40—C46—H46C	109.5
C5—C6—H6A	109.5	H46A—C46—H46C	109.5
C5—C6—H6B	109.5	H46B—C46—H46C	109.5
H6A—C6—H6B	109.5	N16—C47—C48	110.2 (4)
C5—C6—H6C	109.5	N16—C47—C50	119.4 (4)
H6A—C6—H6C	109.5	C48—C47—C50	130.3 (4)
H6B—C6—H6C	109.5	C49—C48—C47	105.4 (4)
C5—C7—H7A	109.5	C49—C48—H48	127.3
C5—C7—H7B	109.5	C47—C48—H48	127.3
H7A—C7—H7B	109.5	N17—C49—C48	107.5 (4)
C5—C7—H7C	109.5	N17—C49—C55	123.0 (4)
H7A—C7—H7C	109.5	C48—C49—C55	129.4 (4)
H7B—C7—H7C	109.5	O7—C50—N18	123.5 (4)
C5—C8—H8C	109.5	O7—C50—C47	121.6 (4)
C5—C8—H8D	109.5	N18—C50—C47	114.9 (4)
H8C—C8—H8D	109.5	N18—C51—C53	109.9 (5)
C5—C8—H8E	109.5	N18—C51—C54	109.9 (5)
H8C—C8—H8E	109.5	C53—C51—C54	111.2 (6)
H8D—C8—H8E	109.5	N18—C51—C52	107.0 (4)
C3—C9—H9A	109.5	C53—C51—C52	108.7 (6)
C3—C9—H9B	109.5	C54—C51—C52	110.1 (6)
H9A—C9—H9B	109.5	C51—C52—H52A	109.5
C3—C9—H9C	109.5	C51—C52—H52B	109.5
H9A—C9—H9C	109.5	H52A—C52—H52B	109.5
H9B—C9—H9C	109.5	C51—C52—H52C	109.5
N3—C10—C11	109.9 (4)	H52A—C52—H52C	109.5
N3—C10—C13	120.2 (4)	H52B—C52—H52C	109.5
C11—C10—C13	129.9 (4)	C51—C53—H53A	109.5
C12—C11—C10	106.1 (4)	C51—C53—H53B	109.5
C12—C11—H11	126.9	H53A—C53—H53B	109.5
C10—C11—H11	126.9	C51—C53—H53C	109.5
C11—C12—N4	107.5 (4)	H53A—C53—H53C	109.5
C11—C12—C18	130.2 (5)	H53B—C53—H53C	109.5
N4—C12—C18	122.3 (4)	C51—C54—H54A	109.5
O2—C13—N8	126.1 (5)	C51—C54—H54B	109.5
O2—C13—C10	121.2 (5)	H54A—C54—H54B	109.5
N8—C13—C10	112.7 (4)	C51—C54—H54C	109.5
N8—C14—C16	109.1 (5)	H54A—C54—H54C	109.5
N8—C14—C17	108.9 (5)	H54B—C54—H54C	109.5
C16—C14—C17	112.2 (6)	C49—C55—H55A	109.5
N8—C14—C15	105.3 (5)	C49—C55—H55B	109.5
C16—C14—C15	111.9 (6)	H55A—C55—H55B	109.5
C17—C14—C15	109.2 (5)	C49—C55—H55C	109.5
C14—C15—H15A	109.5	H55A—C55—H55C	109.5
C14—C15—H15B	109.5	H55B—C55—H55C	109.5
H15A—C15—H15B	109.5	O8—C56—Cu2	172.6 (4)
C14—C15—H15C	109.5	C104—O100—C101	107.7 (14)
H15A—C15—H15C	109.5	O100—C101—C102	104.2 (13)
H15B—C15—H15C	109.5	O100—C101—H10A	110.9
C14—C16—H16A	109.5	C102—C101—H10A	110.9
C14—C16—H16B	109.5	O100—C101—H10B	110.9
H16A—C16—H16B	109.5	C102—C101—H10B	110.9
C14—C16—H16C	109.5	H10A—C101—H10B	108.9
H16A—C16—H16C	109.5	C101—C102—C103	89.9 (12)
H16B—C16—H16C	109.5	C101—C102—H10C	113.7
C14—C17—H17A	109.5	C103—C102—H10C	113.7
C14—C17—H17B	109.5	C101—C102—H10D	113.7
H17A—C17—H17B	109.5	C103—C102—H10D	113.7
C14—C17—H17C	109.5	H10C—C102—H10D	110.9
H17A—C17—H17C	109.5	C102—C103—C104	92.3 (12)
H17B—C17—H17C	109.5	C102—C103—H10E	113.2
C12—C18—H18A	109.5	C104—C103—H10E	113.2
C12—C18—H18B	109.5	C102—C103—H10F	113.2
H18A—C18—H18B	109.5	C104—C103—H10F	113.2
C12—C18—H18C	109.5	H10E—C103—H10F	110.6
H18A—C18—H18C	109.5	O100—C104—C103	106.1 (11)
H18B—C18—H18C	109.5	O100—C104—H10G	110.5
N5—C19—C20	110.8 (4)	C103—C104—H10G	110.5
N5—C19—C22	118.6 (4)	O100—C104—H10H	110.5
C20—C19—C22	130.6 (4)	C103—C104—H10H	110.5
C21—C20—C19	105.3 (4)	H10G—C104—H10H	108.7
C21—C20—H20	127.3	C204—O200—C201	108.2 (17)
C19—C20—H20	127.3	O200—C201—C202	103.5 (14)
N6—C21—C20	107.2 (4)	O200—C201—H20A	111.1
N6—C21—C27	122.8 (4)	C202—C201—H20A	111.1
C20—C21—C27	130.0 (5)	O200—C201—H20B	111.1
O3—C22—N9	124.2 (5)	C202—C201—H20B	111.1
O3—C22—C19	120.9 (4)	H20A—C201—H20B	109.0
N9—C22—C19	114.9 (4)	C201—C202—C203	84.5 (13)
N9—C23—C26	109.4 (6)	C201—C202—H20C	114.6
N9—C23—C24	107.4 (6)	C203—C202—H20C	114.6
C26—C23—C24	108.4 (7)	C201—C202—H20D	114.6
N9—C23—C25	111.3 (5)	C203—C202—H20D	114.6
C26—C23—C25	111.1 (7)	H20C—C202—H20D	111.7
C24—C23—C25	109.1 (7)	C202—C203—C204	81.4 (11)
C23—C24—H24A	109.5	C202—C203—H20E	115.0
C23—C24—H24B	109.5	C204—C203—H20E	115.0
H24A—C24—H24B	109.5	C202—C203—H20F	115.0
C23—C24—H24C	109.5	C204—C203—H20F	115.0
H24A—C24—H24C	109.5	H20E—C203—H20F	112.1
H24B—C24—H24C	109.5	O200—C204—C203	99.1 (14)
C23—C25—H25A	109.5	O200—C204—H20G	112.0
C23—C25—H25B	109.5	C203—C204—H20G	112.0
H25A—C25—H25B	109.5	O200—C204—H20H	112.0
C23—C25—H25C	109.5	C203—C204—H20H	112.0
H25A—C25—H25C	109.5	H20G—C204—H20H	109.6
C1—N1—N2—C3	−0.5 (5)	N6—N5—C19—C22	−178.4 (4)
Cu1—N1—N2—C3	171.1 (3)	Cu1—N5—C19—C22	5.2 (7)
C1—N1—N2—B1	178.0 (4)	N5—C19—C20—C21	−0.1 (5)
Cu1—N1—N2—B1	−10.4 (5)	C22—C19—C20—C21	179.0 (5)
N4—B1—N2—C3	126.1 (5)	N5—N6—C21—C20	1.2 (5)
N6—B1—N2—C3	−114.6 (5)	B1—N6—C21—C20	−178.3 (5)
N4—B1—N2—N1	−52.1 (5)	N5—N6—C21—C27	−179.3 (5)
N6—B1—N2—N1	67.2 (5)	B1—N6—C21—C27	1.2 (8)
C10—N3—N4—C12	0.4 (5)	C19—C20—C21—N6	−0.7 (5)
Cu1—N3—N4—C12	−173.7 (3)	C19—C20—C21—C27	179.9 (5)
C10—N3—N4—B1	176.1 (4)	C23—N9—C22—O3	11.5 (8)
Cu1—N3—N4—B1	2.0 (5)	C23—N9—C22—C19	−169.3 (5)
N6—B1—N4—N3	−61.1 (5)	N5—C19—C22—O3	−52.7 (6)
N2—B1—N4—N3	57.8 (5)	C20—C19—C22—O3	128.2 (6)
N6—B1—N4—C12	113.6 (5)	N5—C19—C22—N9	128.2 (5)
N2—B1—N4—C12	−127.5 (5)	C20—C19—C22—N9	−50.9 (7)
C19—N5—N6—C21	−1.3 (5)	C22—N9—C23—C26	59.0 (8)
Cu1—N5—N6—C21	176.0 (3)	C22—N9—C23—C24	176.5 (7)
C19—N5—N6—B1	178.3 (4)	C22—N9—C23—C25	−64.2 (8)
Cu1—N5—N6—B1	−4.4 (5)	N11—N10—C29—C30	0.0 (5)
N4—B1—N6—N5	62.2 (5)	Cu2—N10—C29—C30	179.7 (3)
N2—B1—N6—N5	−57.0 (5)	N11—N10—C29—C32	176.7 (4)
N4—B1—N6—C21	−118.4 (5)	Cu2—N10—C29—C32	−3.6 (7)
N2—B1—N6—C21	122.5 (5)	N10—C29—C30—C31	0.3 (5)
C29—N10—N11—C31	−0.3 (4)	C32—C29—C30—C31	−175.9 (4)
Cu2—N10—N11—C31	179.9 (3)	N10—N11—C31—C30	0.5 (5)
C29—N10—N11—B2	176.2 (3)	B2—N11—C31—C30	−175.6 (4)
Cu2—N10—N11—B2	−3.5 (4)	N10—N11—C31—C37	−178.0 (4)
N17—B2—N11—C31	117.8 (5)	B2—N11—C31—C37	5.9 (7)
N14—B2—N11—C31	−123.1 (5)	C29—C30—C31—N11	−0.5 (5)
N17—B2—N11—N10	−57.9 (5)	C29—C30—C31—C37	177.9 (5)
N14—B2—N11—N10	61.1 (5)	C33—N12—C32—O5	−1.1 (8)
C38—N13—N14—C40	−0.3 (5)	C33—N12—C32—C29	177.7 (4)
Cu2—N13—N14—C40	175.3 (3)	N10—C29—C32—O5	−24.1 (6)
C38—N13—N14—B2	178.0 (4)	C30—C29—C32—O5	151.8 (5)
Cu2—N13—N14—B2	−6.4 (5)	N10—C29—C32—N12	157.0 (4)
N11—B2—N14—C40	122.4 (4)	C30—C29—C32—N12	−27.0 (7)
N17—B2—N14—C40	−118.5 (5)	C32—N12—C33—C36	−63.2 (7)
N11—B2—N14—N13	−55.5 (5)	C32—N12—C33—C35	59.3 (6)
N17—B2—N14—N13	63.5 (5)	C32—N12—C33—C34	178.5 (5)
C47—N16—N17—C49	−0.2 (5)	N14—N13—C38—C39	0.3 (5)
Cu2—N16—N17—C49	171.1 (3)	Cu2—N13—C38—C39	−173.0 (4)
C47—N16—N17—B2	−178.6 (4)	N14—N13—C38—C41	179.6 (4)
Cu2—N16—N17—B2	−7.3 (5)	Cu2—N13—C38—C41	6.3 (8)
N11—B2—N17—N16	65.5 (5)	N13—C38—C39—C40	−0.2 (5)
N14—B2—N17—N16	−53.6 (5)	C41—C38—C39—C40	−179.5 (4)
N11—B2—N17—C49	−112.6 (5)	N13—N14—C40—C39	0.1 (5)
N14—B2—N17—C49	128.3 (4)	B2—N14—C40—C39	−178.0 (4)
N2—N1—C1—C2	0.0 (6)	N13—N14—C40—C46	−179.5 (4)
Cu1—N1—C1—C2	−168.0 (4)	B2—N14—C40—C46	2.3 (7)
N2—N1—C1—C4	−175.8 (5)	C38—C39—C40—N14	0.0 (5)
Cu1—N1—C1—C4	16.2 (9)	C38—C39—C40—C46	179.7 (5)
N1—C1—C2—C3	0.6 (6)	C42—N15—C41—O6	0.4 (7)
C4—C1—C2—C3	176.3 (5)	C42—N15—C41—C38	179.9 (4)
N1—N2—C3—C2	0.9 (6)	N13—C38—C41—O6	177.0 (4)
B1—N2—C3—C2	−177.5 (5)	C39—C38—C41—O6	−3.8 (7)
N1—N2—C3—C9	−179.5 (6)	N13—C38—C41—N15	−2.5 (6)
B1—N2—C3—C9	2.1 (9)	C39—C38—C41—N15	176.7 (4)
C1—C2—C3—N2	−0.9 (7)	C41—N15—C42—C43	−64.6 (6)
C1—C2—C3—C9	179.6 (7)	C41—N15—C42—C45	176.7 (4)
C5—N7—C4—O1	3.1 (10)	C41—N15—C42—C44	58.6 (6)
C5—N7—C4—C1	179.5 (6)	N17—N16—C47—C48	−0.1 (5)
N1—C1—C4—O1	−162.9 (5)	Cu2—N16—C47—C48	−168.0 (3)
C2—C1—C4—O1	22.0 (9)	N17—N16—C47—C50	178.6 (3)
N1—C1—C4—N7	20.5 (8)	Cu2—N16—C47—C50	10.7 (6)
C2—C1—C4—N7	−154.6 (6)	N16—C47—C48—C49	0.3 (5)
C4—N7—C5—C7	62.6 (8)	C50—C47—C48—C49	−178.2 (4)
C4—N7—C5—C8	−177.8 (7)	N16—N17—C49—C48	0.3 (5)
C4—N7—C5—C6	−59.6 (10)	B2—N17—C49—C48	178.5 (4)
N4—N3—C10—C11	0.3 (5)	N16—N17—C49—C55	−178.9 (4)
Cu1—N3—C10—C11	172.3 (3)	B2—N17—C49—C55	−0.7 (7)
N4—N3—C10—C13	−177.4 (4)	C47—C48—C49—N17	−0.4 (5)
Cu1—N3—C10—C13	−5.4 (7)	C47—C48—C49—C55	178.8 (4)
N3—C10—C11—C12	−0.8 (5)	C51—N18—C50—O7	0.4 (8)
C13—C10—C11—C12	176.6 (4)	C51—N18—C50—C47	179.8 (5)
C10—C11—C12—N4	1.0 (5)	N16—C47—C50—O7	14.0 (6)
C10—C11—C12—C18	−177.5 (5)	C48—C47—C50—O7	−167.6 (4)
N3—N4—C12—C11	−0.9 (5)	N16—C47—C50—N18	−165.3 (4)
B1—N4—C12—C11	−176.0 (4)	C48—C47—C50—N18	13.0 (7)
N3—N4—C12—C18	177.7 (4)	C50—N18—C51—C53	63.0 (7)
B1—N4—C12—C18	2.6 (7)	C50—N18—C51—C54	−59.7 (7)
C14—N8—C13—O2	4.2 (8)	C50—N18—C51—C52	−179.1 (6)
C14—N8—C13—C10	−177.5 (4)	C104—O100—C101—C102	31 (2)
N3—C10—C13—O2	−29.6 (7)	O100—C101—C102—C103	−56 (2)
C11—C10—C13—O2	153.2 (5)	C101—C102—C103—C104	54.3 (17)
N3—C10—C13—N8	152.0 (4)	C101—O100—C104—C103	9 (2)
C11—C10—C13—N8	−25.2 (7)	C102—C103—C104—O100	−44 (2)
C13—N8—C14—C16	66.8 (7)	C204—O200—C201—C202	18 (3)
C13—N8—C14—C17	−55.9 (7)	O200—C201—C202—C203	−60 (2)
C13—N8—C14—C15	−172.9 (5)	C201—C202—C203—C204	64.6 (14)
N6—N5—C19—C20	0.9 (5)	C201—O200—C204—C203	31 (2)
Cu1—N5—C19—C20	−175.5 (4)	C202—C203—C204—O200	−65.2 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7···N1	0.84 (3)	2.46 (6)	2.868 (6)	111 (5)
N8—H8···O6	0.86 (3)	2.17 (3)	3.013 (5)	165 (5)
N9—H9···O1^i	0.84 (3)	2.12 (4)	2.921 (6)	159 (5)
N12—H12···O3^ii	0.85 (3)	2.35 (3)	3.140 (5)	157 (5)
N15—H15···N13	0.84 (3)	2.52 (5)	2.923 (5)	110 (4)
N18—H18···O5^ii	0.85 (3)	2.31 (3)	3.127 (5)	162 (5)

Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) −x+2, y+1/2, −z+3/2.