(N,N-Di­ethyl­dithio­carbamato)[tris­(3,5-di­methyl­pyrazol-1-yl)hydro­borato]copper(II): a new copper(II) di­thio­carbamate compound with the classic Tp^Me₂ scorpionate

The title complex, [Cu(C₅H₁₀NS₂)(C₁₅H₂₂BN₆)] or (Tp^Me₂)Cu(S₂CNEt₂), incorporating the classic Tp^Me₂ scorpionate, is relevant to blue copper protein models and to Cu extraction from waste treatment and mine-tailing leachate. The IR and UV-Vis spectra are consistent with the crystal structure.

S1. Introduction

Extraction studies revealed that the first-generation tetra­kis(pyrazol-1-yl)borate ligand can selectively extract Mg²⁺ but not Ca²⁺ at near neutral pH (Sohrin et al., 1993), while another classic ligand, tris­(3,5-di­methyl­pyrazol-1-yl)hydro­borate (Tp^Me₂), selectively extracted Ca²⁺ and not Mg²⁺ (Sohrin et al., 1994); such differentiation is not achieved using conventional ligands such as ethyl­enedi­amine­tetra­acetic acid (edta). Second-generation tris- and tetra­kis(pyrazolyl)borate ligands were employed to selectively extract transition metals. Tris(3-iso­propyl­pyrazol-1-yl)hydro­borate (Tp^i-Pr), for instance, extracted Cu²⁺, Zn²⁺, and Ni²⁺, and to some extent Co²⁺ and Cd²⁺, but not Mn²⁺ and Fe²⁺. Tetra­kis(3-iso­propyl­pyrazol-1-yl)borate (pz^i-PrTp^i-Pr), on the other hand, complexed Cu²⁺ and Zn²⁺, but not Ni²⁺, Co²⁺, and Cd²⁺. The presence of bulky substituents in the 3- and 5-positions of the pyrazole ring control stability of the compounds, which in turn, di­cta­ted selectivity of extraction (Kitano et al., 2001).

S2. Experimental

S2.1. Synthesis and crystallization

The precursor Cu(S₂CNEt₂)₂ was synthesized according to literature methods (Petrova & Makhaev, 2007). The synthesis of Tp^Me₂Cu(S₂CNEt₂) was carried out using slight modifications of the literature procedure (Halcrow et al., 1997). Stoichiometric amounts of Cu(S₂CNEt₂)₂ and KTp^Me₂ were stirred in benzene for 4 h at room temperature and filtered. The filtrate was evaporated to dryness, the crude product was collected, and purified by silica-gel column chromatography with benzene. Slow evaporation of the eluent produced dark-green crystals (yield 96.9%).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. One of the di­thio­carbamate S atoms was disordered over two positions and was treated with equal atomic displacement parameters and a refined site-occupancy ratio of 88:12. Cu—S and S—C distances for the thiol­ate were restrained to be similar by use of SHELXL SADI commands. H atoms were placed in calculated positions with isotropic displacement parameters set at either 1.2 or 1.5 (for methyl H atoms) of the U_eq values of the attached atom.

S3. Results and discussion

Our initial inter­est in the selective extraction of first-row transition metals using KTp^Me₂ was motivated by potential applications in metallurgy and waste treatment. We found that Co²⁺, Ni²⁺, and Cu²⁺ were separately extracted under different conditions, i.e., reaction times, extraction times, counter-ions, and pH. While 1:2 metal–ligand ratios were determined for Co²⁺ and Ni²⁺, a 1:1 ratio was found for Cu²⁺–Tp^Me₂ when solution pH was adjusted using acetic, hydro­chloric, nitric, and sulfuric acids. Direct synthesis of tentatively formulated Tp^Me₂CuX (where X = Cl^-, Br^-, I^-, NO₃^-, CH₃COO^-, acac^-, S₂CNEt₂^-) was demonstrated from metathesis of CuX₂ salts and KTp^Me₂ in MeOH or benzene (Cañada et al., 2011).

Few copper(II) compounds of the type Tp^Me₂CuX are known (Thompson et al., 1977; Fujisawa et al., 2001). Examples include Tp^Me₂Cu^I/II(SR) (where SR = p-nitro­benzene­thiol­ate and O-ethyl cysteinate), which were used as models of blue copper proteins; the Cu^II complexes were unstable above 243 K, and only the corresponding Cu^I complexes were crystallographically characterized (Thompson et al., 1977). Also motivated by copper–nitro­syl inter­actions in proteins relevant to denitrification, Tp^Me₂Cu(NO₂) was synthesized from reaction of excess NO with Tp^Me₂Cu(NO) (Ruggiero et al., 1994). Structural effects of the substituents at the 3- and 5-positions of the pyrazolyl ring were investigated for a series of Tp^R,R'Cu(NO₃) compounds, including Tp^Me₂Cu(NO₃), which was reported to have a bidentate nitrate ligand and a square pyramidal geometry around the copper center (Fujisawa et al., 2001).

Other known [Tp^R,R'CuX]^0,1+ compounds utilized second- or third-generation ligands, i.e.. Tp^i-Pr₂, Tp^t-Bu,i-Pr, Tp^Ph,Me, Tp^t-Bu,Me, Tp^Ph,i-Pr, Tp^t-Bu,H, Tp^Ph,H, Tp^Cy,H, Tp^6-Mepy, where X = Cl^- (Kitajima et al., 1990), H₂O (Humphrey et al., 1999), NO₃^- (Fujisawa et al., 2000; Fujisawa et al., 2001), OH^- (Fujisawa et al., 2000), CH₃COO^- (Chia et al., 2000), and NO₂^- (Lehnert et al., 2007), while several structurally characterized Tp^Me₂CuL motifs were reported for Cu¹⁺ centers (Blake et al., 2002; Kimani et al., 2010; Lim & Holm, 1998; Lobbia et al., 1997, 2004; Pellei et al., 2000; Thompson et al., 1983). Coordinated 3,5-di­methyl­pyrazole resulted in the formation of a Tp^Me₂CuXY-type complex, i.e. trigonal bipyramidal Tp^Me₂CuBr(Hpz^Me₂) (Zhang et al., 2007), and other Tp^R,R'CuXY complexes, where Y = Hpz^R,R' or solvent, typically result from the decomposition of Tp^R,R'CuX; e.g. Tp^PhCu(O₂CMe)(Hpz^Ph), Tp^Ph2CuCl(Hpz^Ph₂) (Chia et al., 2000); Tp^PhCuCl(Hpz^Ph) (Halcrow et al., 1997), and Tp^i-Pr₂CuCl(dmf) (dmf is di­methyl­formamide; Kitajima et al., 1990). Finally, several dinuclear Cu^I,II compounds were also reported utilizing the Tp^Me₂ ligand (Bartolomas et al., 2002; Di Nicola et al., 2008; Kitajima et al., 1991; Marsh et al., 2002; Mealli et al., 1976).

Employing Tp^Me₂ is believed to result in the formation of the bis­(ligand) (Tp^Me₂)₂Cu compound, which was initially synthesized by exposing a methanol solution of (Tp^Me₂Cu)₂O to air (Kitajima et al., 1988); for example, reaction of CuCl₂(2H₂O) with KTp^Me₂ was reported to yield (Tp^Me₂)₂Cu and not Tp^Me₂CuCl, although Tp^i-Pr₂CuCl is formed in moderate yield from metathesis of CuCl₂(2H₂O)) with KTp^i-Pr₂ (Kitajima et al., 1990). Initial reports (Trofimenko, 1967a,b) also indicated that only bis­(ligand) Tp₂M and (Tp^Me₂)₂M compounds are formed. Second- and third-generation Tp^R,R'CuX complexes (see above), as well as Tp^Me₂Cu(SR) (Thompson et al. 1977) and Tp^Me₂Cu(NO₃) (Fujisawa et al., 2001), however, were routinely prepared from metathesis reactions of the pyrazolylborate ligand with the corresponding copper(II) salts. Here, we report the crystal structure of Tp^Me₂Cu(S₂CNEt₂), a hitherto unreported Cu^II compound of the classic Tp^Me₂ ligand, demonstrating that Tp^Me₂CuX compounds may be accessible using appropriate co-ligands.

IR bands typical for compounds with the ligand Tp^Me₂ were observed. Additional bands attributed to the S₂CNEt₂^- ligand were similar to those reported for Cu(S₂CNEt₂)₂ (Trendafilova et al., 1984). Visible spectroscopy in benzene of Tp^Me₂Cu(S₂CNEt₂) revealed two bands; i.e. a λ_max at 627.0 nm with a molar absorptivity value of 420.9 M^-1 cm^-1, and a second band at 405.0 nm, consistent with a d–d transition for a five-coordinate metal center. Four-coordinate Tp^i-Pr₂CuCl was reported to have a band at 996 nm, which shifted to higher energy (758 nm) for five-coordinate Tp^i-Pr₂CuCl(dmf) (Kitajima et al., 1990). Other five-coordinate copper(II) centers showed d–d transitions ranging from 708–797 nm (Halcrow et al., 1997; Fujisawa et al., 2000; Chia et al., 2000). Further shift to higher energies (689 nm) is observed for square-pyramidal Tp^PhCu(O₂CMe)(Hpz^Ph), where the acetate ligand is monodentate (Chia et al., 2000), while solutions of Tp^Me₂Cu(SR) (SR = p-nitro­benzene­thiol­ate and O-ethyl cysteinate) showed intense absorptions at 600–625 nm with molar absorptivity ranging from 1000–5000 M^-1 cm^-1 (Thompson et al., 1977). Finally, square-planar [Tp^2-SMePhCu]PF₆, with an N₃S₂ environment, was reported to have a d–d transition at 630 nm (Humphrey et al. 1999).

A molecular diagram of Tp^Me₂Cu(S₂CNEt₂) is presented in Fig. 1. Selected bond metrics are shown in Table 2. The Cu^II center adopts a distorted square-pyramidal geometry with the basal plane defined by pyrazolylborate atoms N1 and N5, and di­thio­carbamate atoms S1 and S2, and the apical site is occupied by the pyrazolyl N3 atom. As expected, the apical Cu1—N3 bond length is longer than the Cu1—N1 and Cu1—N5 distances. The Cu—S thiol­ate bond lengths are comparable to that observed for the blue copper protein model compound (see below), although a second shorter position was solved for the disordered contribution. Distortion from ideal square-planar geometry is given by τ = 0.37 (Addison et al., 1984), with the Cu^II atom displaced by 0.25 (7) Å from the least-squares plane defined by atoms N1, N5, S1, and S2 towards the apical N3 atom.

Little structural information was given for Tp^Me₂Cu(NO₃) (Fujisawa et al., 2001), while only the tetra­hedral [Tp^Me₂Cu^I(p-NO₂C₆H₄S)]^- was characterized with an Cu—S bond length of 2.19 (1) Å; the corresponding Cu^II compound was unstable above 243 K (Thompson et al., 1977). Key structural features, i.e., τ values, apical Cu—N bond lengths, and displacement of the Cu atom from the basal plane, are consistent with other Cu^II compounds of second- and third-generation pyrazolylborate ligands. For example, Tp^i-Pr₂Cu(NO₃) was reported to have τ = 0.22, while the trigonal pyramidal Tp^t-Bu,i-PrCu(NO₃) had a τ value of 0.77 (Fujisawa et al., 2000). Square-planar [Tp^2-SMePhCu]PF₆, with τ = 0.15, has an N₃S₂ environment where the apical Cu—N bond length is 2.141 (5) Å and the Cu atom deviates by 0.09 Å above the least-squares plane towards the apical ligand (Humphrey et al., 1999), while Tp^i-Pr₂Cu(NO₂), τ = 0.17, has an apical Cu—N bond length of 2.110 (3) Å (Lehnert et al., 2007). Recognition of the role of the co-ligand, e.g. NO^- and NO₂^- (Ruggiero et al., 1994), NO₃^- (Fujisawa et al., 2001), and S₂CNEt₂^- (this work) in formulating strategies for selective extraction of Cu^II using Tp^Me₂ from aqueous solutions may prove useful.

Related literature

For related literature, see: Addison et al. (1984); Bartolomas et al. (2002); Blake et al. (2002); Cañada, Nazareno, Melgo & Lim (2011); Chia et al. (2000); Di Nicola, Marchetti, Monari, Pandolfo & Pettinari (2008); Fujisawa et al. (2000, 2001); Halcrow et al. (1997); Humphrey et al. (1999); Kimani et al. (2010); Kitajima et al. (1988, 1990, 1991); Kitano et al. (2001); Lehnert et al. (2007); Lim & Holm (1998); Lobbia et al. (1997, 2004); Marsh et al. (2002); Mealli et al. (1976); Pellei et al. (2000); Petrova & Makhaev (2007); Ruggiero et al. (1994); Sohrin et al. (1993, 1994); Thompson et al. (1977, 1983); Trendafilova et al. (1984); Trofimenko (1967a, 1967b); Zhang et al. (2007).

Computing details

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: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

The molecular structure of Tp^Me₂Cu(S₂CNEt₂), showing the atom-labeling scheme and displacement ellipsoids at the 50% probability level. Atom S1' and dotted lines represent the minor disordered contribution of atom S1. H atoms are depicted at an arbitrary radius.

(N,N-Diethyldithiocarbamato)[tris(3,5-dimethylpyrazol-1-yl)hydroborato]copper(II)

Crystal data

[Cu(C5H10NS2)(C15H22BN6)]	F(000) = 1068
Mr = 509.00	Dx = 1.370 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6123 reflections
a = 10.9499 (9) Å	θ = 2.4–27.4°
b = 13.4234 (12) Å	µ = 1.08 mm^−1
c = 16.8469 (15) Å	T = 200 K
β = 94.593 (2)°	Block, green
V = 2468.3 (4) Å^3	0.36 × 0.21 × 0.16 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	5598 independent reflections
Radiation source: fine-focus sealed tube	4583 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
Detector resolution: 8.33 pixels mm^-1	θmax = 27.4°, θmin = 1.9°
ϕ and ω scans	h = −12→14
Absorption correction: multi-scan (APEX2; Bruker, 2007)	k = −17→17
Tmin = 0.701, Tmax = 0.847	l = −21→21
24027 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.105	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0561P)^2 + 1.2401P] where P = (Fo^2 + 2Fc^2)/3
5598 reflections	(Δ/σ)max < 0.001
292 parameters	Δρmax = 0.81 e Å^−3
6 restraints	Δρmin = −0.34 e Å^−3

Special details

Experimental. All reagents and solvents were analytical grade or better and were used as received and all reactions were performed in air at ambient conditions. Infrared analysis was carried out using a Perkin-Elmer Spectrum 100 FTIR as KBr disks, while UV-visible spectrometry employed a Shimadzu UV-1601 double-beam spectrophotometer using benzene as solvent.

Infrared (KBr, cm^-1): 2975.3, 2925.6, 2865.9, ν(BH) 2508.8, Tp^Me₂ ν(CN) 1544.6, S₂CNEt₂ ν(CN) 1504.9, 1445.5, 1429.1, 1414.9, 1380.5, 1356.0, 1302.4, 1276.8, 1207.9, 1184.7, 1148.9, 1089.8, 1065.1, 1039.0, 1000.2, 976.4, 914.6, 848.8, 808.3, 780.1, 688.8, 646.5, 464.0. UV-vis; λ, nm (ε, M^-1 cm^-1): 627.0 (420.9), 405.0.

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.

The total exposure time was 15.38 h. The frames were integrated with the Bruker SAINT software package using a narrow-frame algorithm. The integration of the data using a monoclinic unit cell yielded a total of 24027 reflections to a maximum θ angle of 27.44° (0.77 Å resolution), of which 5598 were independent (average redundancy 4.292, completeness = 99.5%, R_int = 3.49%, R_sig = 2.88%) and 4583 (81.87%) were greater than 2σ(F²). The final cell constants of a = 10.9499 (9) Å, b = 13.4234 (12) Å, c = 16.8469 (15) Å, β = 94.593 (2)°, volume = 2468.3 (4) ų, are based upon the refinement of the XYZ-centroids of 6123 reflections above 20 σ(I) with 4.81° < 2θ < 54.84°. Data were corrected for absorption effects using the multi-scan method (SADABS). The ratio of minimum to maximum apparent transmission was 0.841. The calculated minimum and maximum transmission coefficients (based on crystal size) are 0.7007 and 0.8467.

The structure was solved and refined using the Bruker SHELXTL Software Package, using the space group P 1 21/c 1, with Z = 4 for the formula unit, C₂₀H₃₂BCuN₇S₂.

The final anisotropic full-matrix least-squares refinement on F² with 292 variables converged at R1 = 3.73%, for the observed data and wR2 = 10.53% for all data. The goodness-of-fit was 1.032. The largest peak in the final difference electron density synthesis was 0.808 e^-/ų and the largest hole was -0.344 e^-/ų with an RMS deviation of 0.066 e^-/ų. On the basis of the final model, the calculated density was 1.370 g/cm³ and F(000), 1068 e^-.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.25786 (2)	0.095318 (18)	0.160815 (16)	0.02744 (10)
B1	0.0623 (2)	−0.04596 (17)	0.22071 (15)	0.0280 (5)
H1	−0.0023	−0.0927	0.2371	0.034*
S1	0.26790 (6)	0.27050 (5)	0.16756 (11)	0.0374 (3)	0.884 (4)
S1'	0.2703 (5)	0.2639 (4)	0.1279 (8)	0.0374 (3)	0.116 (4)
S2	0.46372 (5)	0.13215 (4)	0.15309 (4)	0.03922 (16)
N1	0.08151 (16)	0.08706 (13)	0.11733 (11)	0.0291 (4)
N2	0.00538 (15)	0.02824 (13)	0.15811 (11)	0.0278 (4)
N3	0.21133 (17)	0.07772 (13)	0.28509 (11)	0.0296 (4)
N4	0.12060 (16)	0.00907 (13)	0.29419 (11)	0.0278 (4)
N5	0.26042 (15)	−0.05685 (13)	0.15230 (10)	0.0259 (4)
N6	0.16337 (16)	−0.10547 (12)	0.18230 (11)	0.0254 (4)
N7	0.50216 (18)	0.32882 (14)	0.16705 (13)	0.0356 (4)
C1	0.0682 (3)	0.1921 (2)	−0.00326 (16)	0.0489 (7)
H1A	0.0198	0.2531	−0.0118	0.073*
H1B	0.0689	0.1555	−0.0535	0.073*
H1C	0.1524	0.2095	0.0160	0.073*
C2	0.0130 (2)	0.12868 (17)	0.05697 (14)	0.0344 (5)
C3	−0.1078 (2)	0.09816 (18)	0.05958 (17)	0.0423 (6)
H3	−0.1756	0.1172	0.0241	0.051*
C4	−0.1100 (2)	0.03499 (17)	0.12354 (15)	0.0350 (5)
C5	−0.2164 (2)	−0.0175 (2)	0.1548 (2)	0.0556 (8)
H5A	−0.2016	−0.0895	0.1551	0.083*
H5B	−0.2909	−0.0026	0.1208	0.083*
H5C	−0.2265	0.0052	0.2092	0.083*
C6	0.3443 (2)	0.1881 (2)	0.37182 (17)	0.0458 (6)
H6A	0.4087	0.1767	0.3357	0.069*
H6B	0.3795	0.1840	0.4271	0.069*
H6C	0.3086	0.2544	0.3620	0.069*
C7	0.2467 (2)	0.11067 (16)	0.35772 (14)	0.0328 (5)
C8	0.1799 (2)	0.06364 (18)	0.41406 (14)	0.0373 (5)
H8	0.1872	0.0739	0.4700	0.045*
C9	0.1011 (2)	−0.00068 (17)	0.37192 (14)	0.0334 (5)
C10	0.0091 (3)	−0.0714 (2)	0.40041 (17)	0.0526 (7)
H10A	0.0258	−0.1387	0.3814	0.079*
H10B	−0.0733	−0.0509	0.3798	0.079*
H10C	0.0145	−0.0711	0.4588	0.079*
C11	0.4440 (2)	−0.10080 (17)	0.08313 (17)	0.0401 (6)
H11A	0.4259	−0.0472	0.0445	0.060*
H11B	0.4728	−0.1596	0.0557	0.060*
H11C	0.5077	−0.0787	0.1235	0.060*
C12	0.3307 (2)	−0.12648 (16)	0.12242 (13)	0.0286 (4)
C13	0.2802 (2)	−0.22031 (16)	0.13365 (14)	0.0341 (5)
H13	0.3120	−0.2826	0.1181	0.041*
C14	0.1752 (2)	−0.20487 (15)	0.17161 (13)	0.0304 (5)
C15	0.0878 (3)	−0.27973 (17)	0.20113 (16)	0.0429 (6)
H15A	0.1128	−0.3469	0.1864	0.064*
H15B	0.0050	−0.2662	0.1771	0.064*
H15C	0.0885	−0.2750	0.2592	0.064*
C16	0.4223 (2)	0.25440 (15)	0.16121 (14)	0.0307 (5)
C17	0.4630 (3)	0.4321 (2)	0.18410 (18)	0.0504 (7)
H17A	0.5321	0.4684	0.2125	0.061*
H17B	0.3949	0.4299	0.2193	0.061*
C18	0.4221 (4)	0.4869 (3)	0.1095 (3)	0.0831 (12)
H18A	0.4921	0.4966	0.0775	0.125*
H18B	0.3887	0.5519	0.1231	0.125*
H18C	0.3587	0.4482	0.0789	0.125*
C19	0.6326 (2)	0.31270 (18)	0.15625 (15)	0.0381 (5)
H19A	0.6578	0.2477	0.1800	0.046*
H19B	0.6812	0.3651	0.1856	0.046*
C20	0.6621 (3)	0.3139 (3)	0.0711 (2)	0.0642 (9)
H20A	0.6114	0.2647	0.0409	0.096*
H20B	0.7489	0.2976	0.0680	0.096*
H20C	0.6456	0.3804	0.0487	0.096*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02103 (15)	0.01757 (14)	0.04435 (18)	−0.00129 (9)	0.00659 (11)	0.00227 (10)
B1	0.0228 (11)	0.0231 (11)	0.0387 (13)	−0.0058 (9)	0.0059 (10)	0.0012 (9)
S1	0.0257 (3)	0.0202 (3)	0.0675 (10)	0.0005 (2)	0.0119 (4)	0.0001 (4)
S1'	0.0257 (3)	0.0202 (3)	0.0675 (10)	0.0005 (2)	0.0119 (4)	0.0001 (4)
S2	0.0248 (3)	0.0210 (3)	0.0732 (4)	−0.0007 (2)	0.0119 (3)	0.0015 (3)
N1	0.0255 (9)	0.0231 (8)	0.0385 (10)	−0.0001 (7)	0.0023 (8)	0.0039 (7)
N2	0.0203 (8)	0.0242 (9)	0.0390 (10)	−0.0030 (7)	0.0035 (7)	0.0002 (7)
N3	0.0252 (9)	0.0258 (9)	0.0383 (10)	−0.0062 (7)	0.0050 (8)	−0.0027 (7)
N4	0.0241 (9)	0.0249 (9)	0.0349 (10)	−0.0048 (7)	0.0055 (7)	0.0008 (7)
N5	0.0209 (9)	0.0208 (8)	0.0360 (10)	−0.0010 (6)	0.0033 (7)	−0.0002 (7)
N6	0.0246 (9)	0.0179 (8)	0.0337 (9)	−0.0037 (6)	0.0014 (7)	0.0012 (7)
N7	0.0295 (10)	0.0261 (9)	0.0512 (12)	−0.0061 (8)	0.0033 (9)	0.0027 (8)
C1	0.0659 (19)	0.0378 (14)	0.0427 (14)	0.0039 (12)	0.0027 (13)	0.0090 (11)
C2	0.0392 (13)	0.0257 (10)	0.0378 (12)	0.0058 (9)	−0.0008 (10)	−0.0013 (9)
C3	0.0335 (13)	0.0374 (13)	0.0532 (15)	0.0068 (10)	−0.0130 (11)	−0.0015 (11)
C4	0.0209 (10)	0.0315 (11)	0.0519 (14)	0.0021 (9)	−0.0014 (10)	−0.0083 (10)
C5	0.0210 (12)	0.0538 (17)	0.092 (2)	−0.0052 (11)	0.0048 (13)	−0.0006 (15)
C6	0.0410 (14)	0.0418 (14)	0.0540 (16)	−0.0103 (11)	0.0006 (12)	−0.0124 (12)
C7	0.0271 (12)	0.0285 (11)	0.0424 (13)	0.0006 (8)	0.0011 (10)	−0.0071 (9)
C8	0.0400 (13)	0.0378 (12)	0.0342 (12)	−0.0010 (10)	0.0045 (10)	−0.0059 (10)
C9	0.0333 (12)	0.0313 (11)	0.0365 (12)	−0.0003 (9)	0.0086 (9)	−0.0002 (9)
C10	0.0640 (19)	0.0538 (16)	0.0429 (15)	−0.0200 (14)	0.0224 (13)	−0.0018 (12)
C11	0.0342 (13)	0.0322 (12)	0.0553 (15)	0.0031 (9)	0.0127 (11)	−0.0088 (10)
C12	0.0274 (11)	0.0239 (10)	0.0341 (11)	0.0039 (8)	−0.0002 (9)	−0.0014 (8)
C13	0.0425 (13)	0.0198 (10)	0.0395 (12)	0.0053 (9)	0.0003 (10)	−0.0019 (9)
C14	0.0385 (12)	0.0191 (9)	0.0325 (11)	−0.0028 (9)	−0.0045 (9)	0.0032 (8)
C15	0.0553 (16)	0.0230 (11)	0.0504 (15)	−0.0108 (10)	0.0042 (12)	0.0050 (10)
C16	0.0276 (11)	0.0232 (10)	0.0415 (12)	−0.0019 (8)	0.0050 (9)	0.0037 (9)
C17	0.0518 (17)	0.0345 (13)	0.0655 (18)	−0.0113 (12)	0.0081 (14)	−0.0071 (12)
C18	0.089 (3)	0.0458 (19)	0.111 (3)	0.0032 (18)	−0.013 (2)	0.0150 (19)
C19	0.0275 (12)	0.0350 (12)	0.0511 (14)	−0.0099 (9)	−0.0010 (10)	−0.0009 (10)
C20	0.061 (2)	0.066 (2)	0.069 (2)	−0.0193 (16)	0.0249 (16)	−0.0194 (16)

Geometric parameters (Å, º)

Cu1—N1	2.0128 (18)	C5—H5C	0.9800
Cu1—N3	2.2067 (19)	C6—C7	1.496 (3)
Cu1—N5	2.0480 (18)	C6—H6A	0.9800
Cu1—S2	2.3215 (6)	C6—H6B	0.9800
Cu1—S1'	2.336 (6)	C6—H6C	0.9800
Cu1—S1	2.3564 (8)	C7—C8	1.395 (3)
B1—N4	1.536 (3)	C8—C9	1.377 (3)
B1—N2	1.545 (3)	C8—H8	0.9500
B1—N6	1.548 (3)	C9—C10	1.491 (3)
B1—H1	1.0000	C10—H10A	0.9800
S1—C16	1.716 (2)	C10—H10B	0.9800
S1'—C16	1.719 (7)	C10—H10C	0.9800
S2—C16	1.711 (2)	C11—C12	1.493 (3)
N1—C2	1.337 (3)	C11—H11A	0.9800
N1—N2	1.372 (2)	C11—H11B	0.9800
N2—C4	1.352 (3)	C11—H11C	0.9800
N3—C7	1.329 (3)	C12—C13	1.395 (3)
N3—N4	1.373 (2)	C13—C14	1.375 (3)
N4—C9	1.350 (3)	C13—H13	0.9500
N5—C12	1.335 (3)	C14—C15	1.500 (3)
N5—N6	1.377 (2)	C15—H15A	0.9800
N6—C14	1.354 (3)	C15—H15B	0.9800
N7—C16	1.326 (3)	C15—H15C	0.9800
N7—C19	1.470 (3)	C17—C18	1.493 (5)
N7—C17	1.487 (3)	C17—H17A	0.9900
C1—C2	1.490 (4)	C17—H17B	0.9900
C1—H1A	0.9800	C18—H18A	0.9800
C1—H1B	0.9800	C18—H18B	0.9800
C1—H1C	0.9800	C18—H18C	0.9800
C2—C3	1.389 (4)	C19—C20	1.495 (4)
C3—C4	1.373 (4)	C19—H19A	0.9900
C3—H3	0.9500	C19—H19B	0.9900
C4—C5	1.493 (3)	C20—H20A	0.9800
C5—H5A	0.9800	C20—H20B	0.9800
C5—H5B	0.9800	C20—H20C	0.9800
N1—Cu1—N5	86.43 (7)	C7—C6—H6C	109.5
N1—Cu1—N3	92.97 (7)	H6A—C6—H6C	109.5
N5—Cu1—N3	88.01 (7)	H6B—C6—H6C	109.5
N1—Cu1—S1	96.44 (5)	N3—C7—C8	110.2 (2)
N5—Cu1—S1	176.23 (5)	N3—C7—C6	121.9 (2)
N3—Cu1—S1	94.27 (6)	C8—C7—C6	127.8 (2)
N1—Cu1—S1'	92.25 (17)	C9—C8—C7	105.9 (2)
N5—Cu1—S1'	161.4 (3)	C9—C8—H8	127.0
N3—Cu1—S1'	110.6 (3)	C7—C8—H8	127.0
S2—Cu1—S1'	72.85 (15)	N4—C9—C8	107.3 (2)
S2—Cu1—S1	75.43 (2)	N4—C9—C10	122.5 (2)
N1—Cu1—S2	154.01 (6)	C8—C9—C10	130.1 (2)
N5—Cu1—S2	100.93 (5)	C9—C10—H10A	109.5
N3—Cu1—S2	112.02 (5)	C9—C10—H10B	109.5
N4—B1—N2	111.04 (17)	H10A—C10—H10B	109.5
N4—B1—N6	108.69 (17)	C9—C10—H10C	109.5
N2—B1—N6	108.07 (17)	H10A—C10—H10C	109.5
N4—B1—H1	109.7	H10B—C10—H10C	109.5
N2—B1—H1	109.7	C12—C11—H11A	109.5
N6—B1—H1	109.7	C12—C11—H11B	109.5
C16—S1—Cu1	85.05 (8)	H11A—C11—H11B	109.5
C16—S1'—Cu1	85.6 (3)	C12—C11—H11C	109.5
C16—S2—Cu1	86.28 (8)	H11A—C11—H11C	109.5
C2—N1—N2	107.16 (18)	H11B—C11—H11C	109.5
C2—N1—Cu1	135.85 (16)	N5—C12—C13	109.5 (2)
N2—N1—Cu1	116.94 (13)	N5—C12—C11	122.03 (19)
C4—N2—N1	109.29 (18)	C13—C12—C11	128.4 (2)
C4—N2—B1	130.51 (18)	C14—C13—C12	106.40 (19)
N1—N2—B1	118.99 (16)	C14—C13—H13	126.8
C7—N3—N4	106.30 (18)	C12—C13—H13	126.8
C7—N3—Cu1	139.94 (16)	N6—C14—C13	107.65 (19)
N4—N3—Cu1	113.70 (13)	N6—C14—C15	123.1 (2)
C9—N4—N3	110.22 (18)	C13—C14—C15	129.2 (2)
C9—N4—B1	130.34 (18)	C14—C15—H15A	109.5
N3—N4—B1	119.38 (17)	C14—C15—H15B	109.5
C12—N5—N6	106.95 (17)	H15A—C15—H15B	109.5
C12—N5—Cu1	137.44 (15)	C14—C15—H15C	109.5
N6—N5—Cu1	115.57 (12)	H15A—C15—H15C	109.5
C14—N6—N5	109.46 (17)	H15B—C15—H15C	109.5
C14—N6—B1	130.07 (18)	N7—C16—S2	123.45 (17)
N5—N6—B1	120.48 (15)	N7—C16—S1	123.20 (17)
C16—N7—C19	121.42 (19)	S2—C16—S1	113.23 (12)
C16—N7—C17	121.2 (2)	N7—C16—S1'	125.7 (3)
C19—N7—C17	117.36 (19)	S2—C16—S1'	107.5 (3)
C2—C1—H1A	109.5	N7—C17—C18	111.6 (3)
C2—C1—H1B	109.5	N7—C17—H17A	109.3
H1A—C1—H1B	109.5	C18—C17—H17A	109.3
C2—C1—H1C	109.5	N7—C17—H17B	109.3
H1A—C1—H1C	109.5	C18—C17—H17B	109.3
H1B—C1—H1C	109.5	H17A—C17—H17B	108.0
N1—C2—C3	109.3 (2)	C17—C18—H18A	109.5
N1—C2—C1	121.6 (2)	C17—C18—H18B	109.5
C3—C2—C1	129.0 (2)	H18A—C18—H18B	109.5
C4—C3—C2	106.5 (2)	C17—C18—H18C	109.5
C4—C3—H3	126.8	H18A—C18—H18C	109.5
C2—C3—H3	126.8	H18B—C18—H18C	109.5
N2—C4—C3	107.7 (2)	N7—C19—C20	113.8 (2)
N2—C4—C5	123.0 (2)	N7—C19—H19A	108.8
C3—C4—C5	129.2 (2)	C20—C19—H19A	108.8
C4—C5—H5A	109.5	N7—C19—H19B	108.8
C4—C5—H5B	109.5	C20—C19—H19B	108.8
H5A—C5—H5B	109.5	H19A—C19—H19B	107.7
C4—C5—H5C	109.5	C19—C20—H20A	109.5
H5A—C5—H5C	109.5	C19—C20—H20B	109.5
H5B—C5—H5C	109.5	H20A—C20—H20B	109.5
C7—C6—H6A	109.5	C19—C20—H20C	109.5
C7—C6—H6B	109.5	H20A—C20—H20C	109.5
H6A—C6—H6B	109.5	H20B—C20—H20C	109.5
N1—Cu1—S1—C16	−155.55 (11)	Cu1—N5—N6—B1	−1.0 (2)
N3—Cu1—S1—C16	110.97 (11)	N4—B1—N6—C14	117.7 (2)
S2—Cu1—S1—C16	−0.69 (9)	N2—B1—N6—C14	−121.7 (2)
S1'—Cu1—S1—C16	−79.5 (5)	N4—B1—N6—N5	−62.4 (2)
N1—Cu1—S1'—C16	−176.0 (4)	N2—B1—N6—N5	58.2 (2)
N5—Cu1—S1'—C16	−90.5 (7)	N2—N1—C2—C3	1.1 (2)
N3—Cu1—S1'—C16	90.0 (4)	Cu1—N1—C2—C3	−176.22 (17)
S2—Cu1—S1'—C16	−17.7 (3)	N2—N1—C2—C1	−175.7 (2)
S1—Cu1—S1'—C16	78.8 (6)	Cu1—N1—C2—C1	7.0 (4)
N1—Cu1—S2—C16	75.11 (14)	N1—C2—C3—C4	−0.8 (3)
N5—Cu1—S2—C16	179.67 (9)	C1—C2—C3—C4	175.7 (2)
N3—Cu1—S2—C16	−88.04 (9)	N1—N2—C4—C3	0.5 (3)
S1'—Cu1—S2—C16	17.7 (3)	B1—N2—C4—C3	−166.5 (2)
S1—Cu1—S2—C16	0.69 (9)	N1—N2—C4—C5	−178.0 (2)
N5—Cu1—N1—C2	−127.0 (2)	B1—N2—C4—C5	15.0 (4)
N3—Cu1—N1—C2	145.2 (2)	C2—C3—C4—N2	0.2 (3)
S2—Cu1—N1—C2	−19.2 (3)	C2—C3—C4—C5	178.6 (3)
S1'—Cu1—N1—C2	34.5 (4)	N4—N3—C7—C8	0.2 (3)
S1—Cu1—N1—C2	50.6 (2)	Cu1—N3—C7—C8	−176.68 (17)
N5—Cu1—N1—N2	55.93 (14)	N4—N3—C7—C6	−179.3 (2)
N3—Cu1—N1—N2	−31.89 (15)	Cu1—N3—C7—C6	3.8 (4)
S2—Cu1—N1—N2	163.72 (10)	N3—C7—C8—C9	0.1 (3)
S1'—Cu1—N1—N2	−142.6 (3)	C6—C7—C8—C9	179.6 (2)
S1—Cu1—N1—N2	−126.53 (14)	N3—N4—C9—C8	0.6 (3)
C2—N1—N2—C4	−0.9 (2)	B1—N4—C9—C8	177.9 (2)
Cu1—N1—N2—C4	176.93 (14)	N3—N4—C9—C10	−178.9 (2)
C2—N1—N2—B1	167.77 (19)	B1—N4—C9—C10	−1.6 (4)
Cu1—N1—N2—B1	−14.3 (2)	C7—C8—C9—N4	−0.4 (3)
N4—B1—N2—C4	−123.9 (2)	C7—C8—C9—C10	179.0 (3)
N6—B1—N2—C4	117.0 (2)	N6—N5—C12—C13	−0.6 (2)
N4—B1—N2—N1	70.2 (2)	Cu1—N5—C12—C13	−178.10 (16)
N6—B1—N2—N1	−49.0 (2)	N6—N5—C12—C11	178.8 (2)
N1—Cu1—N3—C7	−143.1 (2)	Cu1—N5—C12—C11	1.3 (3)
N5—Cu1—N3—C7	130.6 (2)	N5—C12—C13—C14	0.2 (3)
S2—Cu1—N3—C7	29.6 (3)	C11—C12—C13—C14	−179.1 (2)
S1'—Cu1—N3—C7	−49.6 (3)	N5—N6—C14—C13	−0.6 (2)
S1—Cu1—N3—C7	−46.4 (2)	B1—N6—C14—C13	179.3 (2)
N1—Cu1—N3—N4	40.14 (14)	N5—N6—C14—C15	177.0 (2)
N5—Cu1—N3—N4	−46.17 (14)	B1—N6—C14—C15	−3.1 (3)
S2—Cu1—N3—N4	−147.16 (12)	C12—C13—C14—N6	0.2 (2)
S1'—Cu1—N3—N4	133.7 (2)	C12—C13—C14—C15	−177.2 (2)
S1—Cu1—N3—N4	136.84 (13)	C19—N7—C16—S2	8.3 (3)
C7—N3—N4—C9	−0.5 (2)	C17—N7—C16—S2	−172.26 (19)
Cu1—N3—N4—C9	177.32 (14)	C19—N7—C16—S1	−176.10 (19)
C7—N3—N4—B1	−178.14 (18)	C17—N7—C16—S1	3.4 (3)
Cu1—N3—N4—B1	−0.3 (2)	C19—N7—C16—S1'	−148.6 (6)
N2—B1—N4—C9	124.7 (2)	C17—N7—C16—S1'	30.9 (6)
N6—B1—N4—C9	−116.5 (2)	Cu1—S2—C16—N7	175.0 (2)
N2—B1—N4—N3	−58.2 (2)	Cu1—S2—C16—S1	−1.00 (13)
N6—B1—N4—N3	60.6 (2)	Cu1—S2—C16—S1'	−24.5 (4)
N1—Cu1—N5—C12	130.1 (2)	Cu1—S1—C16—N7	−175.0 (2)
N3—Cu1—N5—C12	−136.8 (2)	Cu1—S1—C16—S2	0.99 (13)
S2—Cu1—N5—C12	−24.7 (2)	Cu1—S1—C16—S1'	80.8 (5)
S1'—Cu1—N5—C12	43.7 (6)	Cu1—S1'—C16—N7	−175.7 (2)
N1—Cu1—N5—N6	−47.21 (14)	Cu1—S1'—C16—S2	24.4 (4)
N3—Cu1—N5—N6	45.89 (14)	Cu1—S1'—C16—S1	−84.1 (5)
S2—Cu1—N5—N6	157.94 (12)	C16—N7—C17—C18	−87.6 (3)
S1'—Cu1—N5—N6	−133.6 (5)	C19—N7—C17—C18	91.9 (3)
C12—N5—N6—C14	0.8 (2)	C16—N7—C19—C20	84.0 (3)
Cu1—N5—N6—C14	178.88 (13)	C17—N7—C19—C20	−95.5 (3)
C12—N5—N6—B1	−179.14 (19)