(1,3-Dimethyl­imidazolidine-2-selone-[kappa]Se)bis­(1,10-phenanthroline-[kappa]²N,N')copper(II) bis­(perchlorate) and bis­(2,2'-bipyridyl-[kappa]²N,N')(imidazolidine-2-thione-[kappa]S)copper(II) bis­(perchlorate)

In the first title salt, [Cu(C₁₂H₈N₂)₂(C₅H₁₀N₂Se)](ClO₄)₂, the Cu^II centre occupies a distorted trigonal-bipyramidal environment defined by four N donors from two 1,10-phenanthroline (phen) ligands and by the Se donor of a 1,3-dimethyl­imidazolidine-2-selone ligand, with the equatorial plane defined by the Se and by two N donors from different phen ligands and the axial sites occupied by the two remaining N donors, one from each phen ligand. The Cu-N distances span the range 1.980 (10)-2.114 (11) Å and the Cu-Se distance is 2.491 (3) Å. Inter­molecular [pi]-[pi] contacts between imidazolidine rings and the central rings of phen ligands generate chains of cations. In the second salt, [Cu(C₁₀H₈N₂)₂(C₃H₆N₂S)](ClO₄)₂, the Cu^II centre occupies a similar dis­torted trigonal-bipyramidal environment comprising four N donors from two 2,2'-bipyridyl (bipy) ligands and an S donor from an imidazolidine-2-thione ligand. The equatorial plane is defined by the S donor and two N donors from different bipy ligands. The Cu-N distances span the range 1.984 (6)-2.069 (7) Å and the Cu-S distance is 2.366 (3) Å. Inter­molecular [pi]-[pi] contacts between imidazolidine and pyridyl rings form chains of cations. A major difference between the two structures is due to the presence in the second complex of two N-H...O hydrogen bonds linking the imidazolidine N-H hydrogen-bond donors to perchlorate O-atom acceptors.

S1. Comment

Copper plays an important role in redox-active metalloproteins where evidence for metal–sulfur coordination is consistent with a chemical environment favouring the copper(I) state (Karlin et al., 1982; Lippard & Berg, 1994). Thio- and seleno-amido ligands, –NR–CS(Se)–, react with copper(II) salts yielding S– and Se-bonded copper(I) complexes. In particular, several copper(I) complexes have been prepared and structurally characterized by reacting ligands such as imidazolidine-, thiazolidine-, benzothiazole- and oxazolidine-2-thione and, when possible, also their -2-selone parent compounds with Cu^II salts (Hussein et al., 1985; Devillanova et al., 1986; Battaglia et al. 1979). One approach to studying the redox and coordination chemistry of Cu^II in the presence of soft reducing S– or Se-ketonic donors is to consider complexes of polydentate ligands containing N atoms in which copper is stabilized in the oxidation state two (McKee, 1993).

To preserve the Cu^II oxidation state in the reaction with thiourea and other reducing ligands, Montenero & Pelizzi (1972) have used as starting material copper(II) chelated complexes with π-acceptor ligands such as 1,10-phenanthroline (phen) and 2,2'-bipyridine (bipy). Here we report the synthesis and structural characterization of (dimethylimidazolidine-2-selone-κSe)bis(1,10-phenanthroline- κ²N,N')copper(II) bis(perchlorate), (I), and bis(2,2'-bipyridyl-κ²N,N')(imidazolidine-2-thione-κS)copper(II) bis(perchlorate), (II).

The Cu^II centre in (I) is coordinated in a distorted trigonal–bipyramidal (TBP) environment by four N donors from the two phen ligands and by an Se atom from the dimethylimidazolidine-2-selone ligand (Fig. 1 [the atom labelling in the phen ligands does not match that in CIF/text; please supply correctly labelled figure]). The equatorial plane is defined by the Se atom and by two N donors (N8A and N8B) from different phen ligands, with angles subtended at Cu1 ranging from 112.5 (3) to 128.8 (3)°. The axial sites are occupied by the two remaining N donors (N1A and N1B) from each phen ligand and the N1A—Cu1—N1B angle is 177.6 (5)°. Owing to the narrow bite angle of the phen ligands (ca 80°) which bridge pairs of axial and equatorial sites, the N1A—Cu1—N1B vector deviates significantly from orthogonality with the equatorial plane. A TBP coordination geometry is not common in the case of Cu^II complexes, particularly when they contain ligands with reducing properties (Barclay et al., 1963; Ferrari et al., 1973, 1975). Thus (I) represents, to our knowledge, the only case of a structurally characterized Cu^II mixed-ligand complex featuring a TBP coordination geometry in which the coordination environment contains an Se-atom donor and chelating ligands such as 1,10-phenanthroline (phen) and 2,2'-bipyridine (bipy) with strong π-conjugation properties.

The Cu—N distances range from 1.980 (10) to 2.114 (11) Å, while the Cu—Se distance is 2.491 (3) Å (Table 1). Each phen ligand participates in one long and one short Cu—N bond to the metal, an asymmetry that we attribute to the steric congestion between the two bidentate ligands. This congestion is also expressed in the high degree of twist between the phen units; the dihedral angle between the least-squares mean planes through the five-membered rings Cu1/N1A/C6A/C7A/N8A and Cu1/N1B/C6B/C7B/N8B is 59.6 (3)°. The N—C—C—N torsion angles are essentially zero, indicating that there is no twisting of this unit in either phen ligand. The dihedral angle between the plane through the dimethylimidazolidine-2-selone ring and that through the phen ligand containing atoms N1A and N8A [16.3 (6)°] is much smaller than the corresponding dihedral angle involving the other phen ligand [57.4 (4)°], and therefore only the former is involved in a possible π–π stacking with the N1A–C6A ring [the centroid–centroid distance is 3.506 (10) Å and the perpendicular distance 3.466 (10) Å].

Intermolecular π–π contacts with a centroid–centroid distance of 3.829 (10) Å between the imidazolidine ring in one cation and the central ring (C5B–C7B/C12B–C14B) of the phen ligand in a neighbouring cation at (1/2 + x, 3/2 - y, -z) (Fig. 2) give rise to chains running along the a axis in (I). The mutual inclination of these rings is only 1.6 (6)° and the perpendicular distance is 3.515 (10) Å.

In (II), the Cu^II centre also occupies a distorted trigonal–bipyramidal (TBP) environment, similarly consisting of four N donors from two bipy ligands but with the fifth site occupied by an S-atom donor from an imidazolidine-2-thione ligand (Fig. 3). The equatorial plane is defined by coordination from the S atom and atoms N1A and N8B from different bipy ligands; the angles subtended at Cu1 occupy a somewhat narrower range between 115.44 (18) and 124.72 (19)°, and the axial donors N1B and N8A subtend an angle of 176.7 (2)° at Cu1. The principal deviation from ideal trigonal–bipyamidal geometry is the result of the narrow bite angle of the bipy ligand; there is a significant deviation from orthogonality between the equatorial plane and the N1B—Cu1—N8A vector.

The Cu—N distances range from 1.984 (6) to 2.069 (7) Å, while the Cu—S distance is 2.366 (3) Å (Table 2). This latter is of the same order of magnitude as that found in Cu^I–thiourea complexes (Okaya & Knobler, 1964), a feature also observed in Cu^II–thiourea complexes containing coordinated bipy or phen-chelating ligands (Ferrari et al., 1973, 1975). This observation suggests charge transfer to the metal centre by the chelating ligands through a π-donor effect. The same pattern of asymmetry seen in (I) appears in the Cu—N distances, and in the twist between the Cu1/N1A/C6A/C7A/N8A and Cu1/N1B/C6B/C7B/N8B rings [61.2 (2)°)]. While the N—C—C—N torsion angle in one ligand is essentially zero as in (I), the value of -7.7 (10)° for N1A—C6A—C7A–N8A indicates a slight twist for the other. There are again marked differences in the dihedral angles between the imidazolidine ring and the five-membered rings formed by the coordination of the two bipy ligands. For the Cu1/N1A/C6A/C7A/N8A ring this angle is 59.2 (2)°, but the lower value of 30.9 (3)° suggests the possibility of π–π interaction between the imidazolidine and C7A–C12A rings; the relevant centroid–centroid distance is 3.559 (7) Å, the perpendicular distance is 3.455 (7) Å and the rings are mutually inclined at 24.1 (3)°.

A major difference between the two structures arises from the presence of imidazolidine N—H hydrogen-bond donors in (II) instead of the NMe groups in (I). This leads to the formation of two N—H···O hydrogen bonds to perchlorate O atoms (Fig. 3 and Table 3).

The imidazolidine ring and a pyridyl ring in two neighbouring cations related by the symmetry operation (2 - x, -1/2 + y, 1/2 - z) are involved in intermolecular π–π contacts with a centroid–centroid distance of 3.820 (10) Å to form chains of cations (Fig. 4) running along the b axis in (II). The rings are inclined to each other at an angle of only 6.7 (6)° and the perpendicular distance is 3.392 (10) Å.

Related literature

For related literature, see: Barclay et al. (1963); Battaglia et al. (1979); Devillanova et al. (1986); Ferrari et al. (1973, 1975); Hussein et al. (1985); Karlin et al. (1982); Lippard & Berg (1994); McKee (1993); Montenero & Pelizzi (1972); Okaya & Knobler (1964).

S2. Experimental

[Cu(phen)₂](ClO₄)₂ and [Cu(bipy)₂](ClO₄)₂ were prepared by reacting Cu(ClO₄)₂ with phen or bipy in 1:2 molar ratio in ethanol. The products separated out of the reaction mixtures and were washed with ethanol and dried under reduced pressure. For the preparation of (I), a solution of N,N'-dimethylimidazolidine-2-selone (30.0 mg, 0.17 mmol) in MeCN (2 ml) was added dropwise at room temperature to a solution of [Cu(phen)₂](ClO₄)₂ (53.0 mg, 0.085 mmol) in MeCN (3 ml). The colour of the reaction mixture turned green immediately. Crystals of the title compound were obtained by slow evaporation of the solvent (52.0 mg 76.5% yield). Analysis found (calculated for C₂₉H₂₆Cl₂CuN₆O₈Se): C 43.20 (43.54), H 3.30 (3.27), N 10.35 (10.50)%. For the preparation of (II), a solution of imidazolidine-2-thione (30.0 mg, 029 mmol) in MeCN (3 ml) was added dropwise at room temperature to a solution of [Cu(bipy)₂](ClO₄)₂ (83.4 mg, 0.145 mmol) in MeCN (3 ml). The colour of the reaction mixture turned green immediately. Crystals of the title compound were obtained by slow evaporation of the solvent (88.0 mg, 89.6% yield). Analysis found (calculated for C₂₃H₂₂Cl₂CuN₆O₈S): C 40.60 (40.81), H 3.25 (3.28), N 12.35 (12.41), S 4.52 (4.74)%.

S3. Refinement

NH and NMe H atoms were located in difference Fourier syntheses. The NH H atoms were then refined subject to an N—H distance restraint of 0.90 (2) Å and with U_iso(H) = 1.2U_eq(N); NMe H atoms were refined as part of a rigid rotating group with U_iso(H) = 1.5U_eq(C). All other H atoms were included in calculated positions and refined using a riding model with U_iso(H) = 1.2U_eq(C). Similarity restraints were applied to the Cl—O distances in (I).

The intermediate value of 0.41 (3) for the Flack parameter of (I) suggests that the crystal selected was a racemic twin with approximately equal amounts of each twin component.

Computing details

For both compounds, data collection: STADI4 (Stoe & Cie, 1996); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: enCIFer (Allen et al., 2004), PLATON (Spek, 2003) and publCIF (Westrip, 2007).

Figures

	Fig. 1. A view of the structure of (I), showing the atom-numbering scheme adopted. The perchlorate anions are not shown. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Chains running along the a axis in (I) are formed via intermolecular π–π contacts of 3.829 (10) Å between the imidazolidine ring in one cation and and the central ring of the phen ligand.
	Fig. 3. A view of the structure of (II), showing the atom-numbering scheme adopted and the N—H···O hydrogen bonds between the imidazolidine ring and the perchlorate anions. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 4. Chains of cations are formed along the a axis in (II) via intermolecular π–π contacts of 3.820 (10) Å between the imidazolidine ring in one cation and a pyridyl ring in a neighbouring cation.

(I) (Dimethylimidazolidine-2-selone-κSe)bis(1,10-phenanthroline- κ²N,N')copper(II) bis(perchlorate)

Crystal data

[Cu(C12H8N2)2(C5H10N2Se)](ClO4)2	F(000) = 1612
Mr = 799.96	Dx = 1.703 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 11.606 (6) Å	θ = 12.5–13.9°
b = 12.155 (2) Å	µ = 2.10 mm^−1
c = 22.120 (4) Å	T = 150 K
V = 3120.5 (18) Å^3	Column, green
Z = 4	0.51 × 0.14 × 0.10 mm

Data collection

Stoe Stadi-4 four-circle diffractometer	2621 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.052
Graphite monochromator	θmax = 25.1°, θmin = 2.5°
ω/θ scans	h = −2→13
Absorption correction: numerical (X-RED; Stoe & Cie, 1996)	k = 0→14
Tmin = 0.700, Tmax = 0.830	l = 0→26
3878 measured reflections	3 standard reflections every 60 min
3511 independent reflections	intensity decay: random variation +−5%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: included in calculated positions, except for N-Me (found from delta-F)
R[F^2 > 2σ(F^2)] = 0.074	H-atom parameters constrained
wR(F^2) = 0.144	w = 1/[σ^2(Fo^2) + 24.56P] where P = (Fo^2 + 2Fc^2)/3
S = 1.23	(Δ/σ)max = 0.001
3511 reflections	Δρmax = 0.80 e Å^−3
427 parameters	Δρmin = −0.67 e Å^−3
147 restraints	Absolute structure: Flack (1983), 780 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.41 (3)

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

	x	y	z	Uiso*/Ueq
Cu1	0.14068 (15)	0.67758 (13)	0.00636 (7)	0.0239 (4)
Se1	−0.06144 (13)	0.65302 (13)	0.04170 (7)	0.0338 (4)
N1	−0.1010 (11)	0.4356 (10)	0.0812 (6)	0.039 (3)
N2	−0.0145 (12)	0.5357 (11)	0.1509 (6)	0.043 (4)
N1A	0.1896 (9)	0.5310 (8)	0.0357 (5)	0.019 (2)
N1B	0.0983 (10)	0.8274 (8)	−0.0236 (4)	0.025 (3)
N8A	0.2523 (10)	0.7291 (9)	0.0764 (5)	0.024 (3)
N8B	0.2065 (9)	0.6641 (9)	−0.0808 (4)	0.024 (3)
C1	−0.0563 (14)	0.5337 (12)	0.0956 (6)	0.029 (3)
C2A	0.1556 (13)	0.4345 (10)	0.0128 (6)	0.031 (3)
H2AA	0.1115	0.4326	−0.0234	0.037*
C2B	0.0425 (13)	0.9058 (10)	0.0051 (6)	0.030 (3)
H2BA	0.0158	0.8904	0.0448	0.035*
C2	−0.0890 (17)	0.3599 (14)	0.1331 (9)	0.069 (6)
H2A	−0.0438	0.2940	0.1219	0.083*
H2B	−0.1654	0.3364	0.1483	0.083*
C3A	0.1854 (12)	0.3347 (11)	0.0425 (6)	0.031 (3)
H3AA	0.1618	0.2663	0.0258	0.038*
C3B	0.0203 (13)	1.0089 (11)	−0.0183 (6)	0.032 (3)
H3BA	−0.0195	1.0628	0.0048	0.038*
C3	−0.0273 (16)	0.4270 (13)	0.1788 (8)	0.052 (5)
H3A	−0.0725	0.4319	0.2167	0.062*
H3B	0.0490	0.3946	0.1881	0.062*
C4A	0.2466 (12)	0.3363 (13)	0.0941 (6)	0.029 (3)
H4AA	0.2664	0.2693	0.1136	0.035*
C4B	0.0572 (13)	1.0311 (11)	−0.0758 (6)	0.027 (3)
H4BA	0.0436	1.1013	−0.0932	0.033*
C4	−0.1544 (16)	0.4001 (15)	0.0252 (8)	0.068 (6)
H4A	−0.1426	0.4564	−0.0059	0.102*
H4B	−0.2371	0.3892	0.0316	0.102*
H4C	−0.1194	0.3308	0.0119	0.102*
C5A	0.2815 (13)	0.4375 (11)	0.1193 (6)	0.027 (3)
C5B	0.1151 (12)	0.9501 (11)	−0.1089 (5)	0.023 (3)
C5	0.0314 (13)	0.6300 (15)	0.1827 (7)	0.051 (5)
H5A	0.0257	0.6953	0.1569	0.077*
H5B	0.1124	0.6166	0.1929	0.077*
H5C	−0.0128	0.6420	0.2199	0.077*
C6A	0.2527 (12)	0.5344 (11)	0.0863 (6)	0.020 (3)
C6B	0.1324 (12)	0.8472 (11)	−0.0803 (5)	0.024 (3)
C7A	0.2863 (12)	0.6382 (11)	0.1097 (6)	0.023 (3)
C7B	0.1887 (12)	0.7625 (10)	−0.1113 (6)	0.021 (3)
C9A	0.2835 (12)	0.8261 (12)	0.0970 (6)	0.031 (3)
H9A	0.2584	0.8896	0.0757	0.037*
C9B	0.2600 (13)	0.5841 (13)	−0.1080 (6)	0.030 (4)
H9B	0.2712	0.5169	−0.0868	0.036*
C10A	0.3509 (13)	0.8409 (12)	0.1480 (6)	0.030 (3)
H10A	0.3740	0.9126	0.1601	0.037*
C10B	0.3021 (13)	0.5930 (12)	−0.1679 (6)	0.032 (4)
H10B	0.3428	0.5335	−0.1858	0.039*
C11A	0.3838 (14)	0.7505 (12)	0.1809 (6)	0.033 (3)
H11A	0.4299	0.7599	0.2161	0.040*
C11B	0.2840 (13)	0.6880 (12)	−0.1999 (6)	0.030 (3)
H11B	0.3096	0.6941	−0.2406	0.036*
C12A	0.3506 (12)	0.6459 (11)	0.1635 (6)	0.029 (3)
C12B	0.2278 (12)	0.7749 (11)	−0.1721 (6)	0.024 (3)
C13A	0.3763 (13)	0.5465 (12)	0.1953 (6)	0.033 (3)
H13A	0.4164	0.5504	0.2327	0.039*
C13B	0.2076 (12)	0.8823 (11)	−0.1986 (6)	0.025 (3)
H13B	0.2321	0.8952	−0.2390	0.031*
C14A	0.3449 (12)	0.4476 (12)	0.1735 (6)	0.028 (3)
H14A	0.3659	0.3830	0.1950	0.034*
C14B	0.1566 (13)	0.9629 (12)	−0.1689 (6)	0.031 (3)
H14B	0.1474	1.0320	−0.1883	0.037*
Cl1	0.0915 (3)	1.0784 (3)	0.14224 (15)	0.0303 (9)
O1	0.1762 (8)	1.0799 (8)	0.0951 (4)	0.036 (3)
O2	0.0995 (11)	0.9775 (7)	0.1751 (5)	0.063 (4)
O3	−0.0213 (7)	1.0883 (9)	0.1163 (5)	0.044 (3)
O4	0.1106 (9)	1.1699 (7)	0.1823 (4)	0.042 (3)
Cl2	0.5385 (3)	0.1680 (3)	0.14352 (16)	0.0367 (9)
O5	0.4999 (10)	0.2082 (8)	0.0860 (4)	0.048 (3)
O6	0.5548 (12)	0.0535 (7)	0.1415 (6)	0.075 (4)
O7	0.4506 (11)	0.1907 (12)	0.1875 (4)	0.090 (6)
O8	0.6399 (12)	0.2210 (12)	0.1618 (6)	0.116 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0288 (9)	0.0211 (8)	0.0217 (8)	0.0049 (9)	0.0008 (8)	0.0019 (7)
Se1	0.0278 (8)	0.0404 (9)	0.0331 (7)	0.0089 (8)	0.0055 (8)	0.0105 (7)
N1	0.026 (8)	0.041 (8)	0.050 (8)	0.002 (7)	0.006 (7)	0.002 (7)
N2	0.036 (8)	0.057 (9)	0.035 (7)	0.004 (8)	−0.003 (7)	0.011 (7)
N1A	0.016 (6)	0.021 (6)	0.020 (5)	−0.007 (5)	−0.003 (5)	−0.001 (5)
N1B	0.036 (7)	0.008 (5)	0.030 (6)	0.006 (6)	−0.002 (5)	0.007 (5)
N8A	0.028 (7)	0.022 (6)	0.024 (6)	0.005 (6)	0.006 (6)	−0.006 (5)
N8B	0.023 (6)	0.026 (6)	0.022 (5)	0.001 (6)	−0.001 (5)	0.002 (6)
C1	0.025 (8)	0.037 (8)	0.024 (7)	0.012 (8)	0.005 (7)	−0.010 (7)
C2A	0.032 (9)	0.028 (7)	0.032 (7)	0.005 (7)	0.000 (7)	−0.004 (6)
C2B	0.035 (9)	0.026 (6)	0.027 (7)	0.016 (7)	0.006 (7)	−0.003 (5)
C2	0.058 (14)	0.032 (10)	0.117 (16)	0.001 (10)	0.010 (12)	0.014 (10)
C3A	0.037 (8)	0.025 (6)	0.038 (6)	0.017 (7)	0.012 (6)	−0.011 (6)
C3B	0.040 (10)	0.028 (6)	0.027 (6)	0.008 (7)	−0.013 (6)	−0.003 (5)
C3	0.050 (12)	0.051 (11)	0.055 (11)	0.019 (9)	0.018 (8)	0.030 (8)
C4A	0.022 (8)	0.029 (5)	0.036 (6)	0.010 (7)	0.016 (5)	0.005 (5)
C4B	0.023 (8)	0.023 (6)	0.035 (6)	−0.001 (6)	−0.013 (6)	0.003 (5)
C4	0.047 (12)	0.061 (12)	0.096 (16)	−0.013 (11)	−0.006 (12)	−0.034 (11)
C5A	0.028 (8)	0.029 (5)	0.025 (6)	0.023 (6)	0.005 (5)	0.000 (5)
C5B	0.023 (8)	0.025 (5)	0.020 (5)	−0.002 (6)	−0.011 (5)	0.009 (4)
C5	0.017 (9)	0.104 (15)	0.032 (8)	−0.002 (10)	0.000 (7)	−0.016 (10)
C6A	0.023 (8)	0.024 (5)	0.013 (6)	0.008 (6)	0.013 (5)	0.001 (4)
C6B	0.024 (7)	0.027 (6)	0.020 (5)	0.003 (7)	−0.003 (5)	0.006 (4)
C7A	0.022 (8)	0.029 (5)	0.019 (6)	−0.009 (6)	0.008 (5)	0.007 (5)
C7B	0.024 (8)	0.018 (5)	0.022 (5)	−0.015 (5)	0.000 (6)	−0.002 (4)
C9A	0.029 (8)	0.026 (8)	0.037 (7)	0.007 (8)	−0.001 (6)	0.001 (7)
C9B	0.035 (9)	0.034 (9)	0.022 (6)	0.002 (8)	0.003 (7)	0.000 (6)
C10A	0.035 (8)	0.027 (5)	0.030 (6)	−0.007 (8)	0.007 (6)	−0.002 (6)
C10B	0.040 (10)	0.029 (6)	0.027 (6)	0.004 (7)	0.015 (7)	−0.008 (5)
C11A	0.035 (10)	0.039 (5)	0.026 (7)	−0.006 (7)	−0.001 (6)	0.002 (5)
C11B	0.032 (9)	0.037 (6)	0.022 (6)	0.000 (7)	0.003 (6)	−0.002 (5)
C12A	0.020 (7)	0.032 (4)	0.035 (7)	0.006 (7)	−0.007 (6)	0.003 (5)
C12B	0.019 (8)	0.031 (5)	0.021 (5)	−0.003 (6)	−0.003 (6)	0.001 (5)
C13A	0.024 (9)	0.042 (5)	0.031 (7)	−0.001 (7)	0.002 (6)	0.014 (5)
C13B	0.013 (7)	0.038 (6)	0.026 (6)	−0.008 (6)	−0.003 (6)	0.010 (5)
C14A	0.018 (8)	0.039 (5)	0.029 (6)	0.001 (7)	0.005 (5)	0.018 (5)
C14B	0.032 (9)	0.031 (6)	0.029 (6)	0.003 (7)	−0.006 (6)	0.016 (5)
Cl1	0.036 (2)	0.0304 (19)	0.0246 (17)	0.0007 (18)	0.0027 (17)	0.0046 (16)
O1	0.049 (7)	0.027 (5)	0.030 (5)	−0.009 (5)	0.019 (5)	−0.001 (5)
O2	0.086 (11)	0.037 (6)	0.066 (8)	0.012 (7)	0.012 (8)	0.028 (6)
O3	0.024 (6)	0.056 (7)	0.052 (7)	−0.003 (6)	−0.008 (5)	−0.017 (6)
O4	0.052 (7)	0.046 (6)	0.027 (5)	−0.011 (7)	−0.003 (5)	−0.013 (5)
Cl2	0.050 (2)	0.0249 (18)	0.0354 (19)	−0.002 (2)	−0.0018 (18)	−0.0006 (17)
O5	0.076 (9)	0.050 (7)	0.017 (5)	0.003 (7)	−0.011 (6)	0.009 (5)
O6	0.098 (11)	0.028 (6)	0.099 (10)	0.027 (8)	−0.001 (10)	0.013 (7)
O7	0.084 (11)	0.141 (14)	0.045 (7)	0.073 (12)	0.011 (8)	−0.003 (9)
O8	0.115 (15)	0.152 (15)	0.083 (10)	−0.086 (14)	−0.027 (11)	0.031 (10)

Geometric parameters (Å, º)

Cu1—N1A	1.980 (10)	C5A—C14A	1.411 (19)
Cu1—N1B	1.999 (10)	C5A—C6A	1.425 (18)
Cu1—N8B	2.080 (10)	C5B—C6B	1.416 (17)
Cu1—N8A	2.114 (11)	C5B—C14B	1.420 (18)
Cu1—Se1	2.491 (3)	C5—H5A	0.9800
Se1—C1	1.878 (14)	C5—H5B	0.9800
N1—C1	1.340 (18)	C5—H5C	0.9800
N1—C4	1.451 (19)	C6A—C7A	1.418 (18)
N1—C2	1.48 (2)	C6B—C7B	1.398 (18)
N2—C1	1.317 (17)	C7A—C12A	1.409 (18)
N2—C5	1.447 (19)	C7B—C12B	1.428 (17)
N2—C3	1.467 (18)	C9A—C10A	1.385 (18)
N1A—C6A	1.337 (16)	C9A—H9A	0.9500
N1A—C2A	1.338 (15)	C9B—C10B	1.417 (18)
N1B—C2B	1.316 (15)	C9B—H9B	0.9500
N1B—C6B	1.336 (14)	C10A—C11A	1.371 (19)
N8A—C9A	1.316 (17)	C10A—H10A	0.9500
N8A—C7A	1.385 (16)	C10B—C11B	1.370 (18)
N8B—C9B	1.301 (17)	C10B—H10B	0.9500
N8B—C7B	1.389 (16)	C11A—C12A	1.384 (19)
C2A—C3A	1.423 (18)	C11A—H11A	0.9500
C2A—H2AA	0.9500	C11B—C12B	1.386 (19)
C2B—C3B	1.380 (17)	C11B—H11B	0.9500
C2B—H2BA	0.9500	C12A—C13A	1.429 (18)
C2—C3	1.48 (2)	C12B—C13B	1.451 (18)
C2—H2A	0.9900	C13A—C14A	1.346 (19)
C2—H2B	0.9900	C13A—H13A	0.9500
C3A—C4A	1.344 (19)	C13B—C14B	1.320 (19)
C3A—H3AA	0.9500	C13B—H13B	0.9500
C3B—C4B	1.370 (18)	C14A—H14A	0.9500
C3B—H3BA	0.9500	C14B—H14B	0.9500
C3—H3A	0.9900	Cl1—O2	1.429 (8)
C3—H3B	0.9900	Cl1—O3	1.434 (8)
C4A—C5A	1.41 (2)	Cl1—O1	1.434 (8)
C4A—H4AA	0.9500	Cl1—O4	1.439 (8)
C4B—C5B	1.399 (18)	Cl2—O8	1.401 (10)
C4B—H4BA	0.9500	Cl2—O6	1.406 (8)
C4—H4A	0.9800	Cl2—O5	1.434 (8)
C4—H4B	0.9800	Cl2—O7	1.437 (9)
C4—H4C	0.9800
N1A—Cu1—N1B	177.6 (5)	C14A—C5A—C6A	119.0 (13)
N1A—Cu1—N8B	97.4 (4)	C4B—C5B—C6B	117.1 (12)
N1B—Cu1—N8B	81.6 (4)	C4B—C5B—C14B	125.1 (12)
N1A—Cu1—N8A	81.4 (4)	C6B—C5B—C14B	117.8 (13)
N1B—Cu1—N8A	97.1 (4)	N2—C5—H5A	109.5
N8B—Cu1—N8A	118.5 (4)	N2—C5—H5B	109.5
N1A—Cu1—Se1	93.4 (3)	H5A—C5—H5B	109.5
N1B—Cu1—Se1	88.9 (3)	N2—C5—H5C	109.5
N8B—Cu1—Se1	128.8 (3)	H5A—C5—H5C	109.5
N8A—Cu1—Se1	112.5 (3)	H5B—C5—H5C	109.5
C1—Se1—Cu1	105.2 (5)	N1A—C6A—C7A	118.9 (12)
C1—N1—C4	129.3 (13)	N1A—C6A—C5A	122.1 (12)
C1—N1—C2	109.5 (13)	C7A—C6A—C5A	118.9 (12)
C4—N1—C2	121.3 (14)	N1B—C6B—C7B	117.7 (12)
C1—N2—C5	127.0 (14)	N1B—C6B—C5B	122.5 (12)
C1—N2—C3	109.7 (14)	C7B—C6B—C5B	119.8 (11)
C5—N2—C3	123.1 (13)	N8A—C7A—C12A	123.2 (12)
C6A—N1A—C2A	120.4 (11)	N8A—C7A—C6A	115.9 (11)
C6A—N1A—Cu1	113.8 (8)	C12A—C7A—C6A	120.9 (12)
C2A—N1A—Cu1	125.5 (9)	N8B—C7B—C6B	117.8 (11)
C2B—N1B—C6B	117.9 (11)	N8B—C7B—C12B	120.0 (12)
C2B—N1B—Cu1	128.4 (9)	C6B—C7B—C12B	122.2 (12)
C6B—N1B—Cu1	113.7 (9)	N8A—C9A—C10A	123.7 (14)
C9A—N8A—C7A	116.9 (11)	N8A—C9A—H9A	118.2
C9A—N8A—Cu1	133.5 (10)	C10A—C9A—H9A	118.2
C7A—N8A—Cu1	109.1 (8)	N8B—C9B—C10B	122.7 (14)
C9B—N8B—C7B	119.4 (11)	N8B—C9B—H9B	118.6
C9B—N8B—Cu1	131.5 (9)	C10B—C9B—H9B	118.6
C7B—N8B—Cu1	109.1 (8)	C11A—C10A—C9A	119.1 (14)
N2—C1—N1	112.3 (13)	C11A—C10A—H10A	120.5
N2—C1—Se1	126.0 (12)	C9A—C10A—H10A	120.5
N1—C1—Se1	121.6 (10)	C11B—C10B—C9B	119.7 (14)
N1A—C2A—C3A	120.0 (13)	C11B—C10B—H10B	120.2
N1A—C2A—H2AA	120.0	C9B—C10B—H10B	120.2
C3A—C2A—H2AA	120.0	C10A—C11A—C12A	120.7 (13)
N1B—C2B—C3B	124.7 (13)	C10A—C11A—H11A	119.7
N1B—C2B—H2BA	117.7	C12A—C11A—H11A	119.7
C3B—C2B—H2BA	117.7	C10B—C11B—C12B	119.0 (13)
N1—C2—C3	103.5 (13)	C10B—C11B—H11B	120.5
N1—C2—H2A	111.1	C12B—C11B—H11B	120.5
C3—C2—H2A	111.1	C11A—C12A—C7A	116.4 (12)
N1—C2—H2B	111.1	C11A—C12A—C13A	125.6 (12)
C3—C2—H2B	111.1	C7A—C12A—C13A	118.1 (13)
H2A—C2—H2B	109.0	C11B—C12B—C7B	119.2 (13)
C4A—C3A—C2A	120.5 (14)	C11B—C12B—C13B	125.7 (13)
C4A—C3A—H3AA	119.7	C7B—C12B—C13B	115.1 (13)
C2A—C3A—H3AA	119.7	C14A—C13A—C12A	121.4 (13)
C4B—C3B—C2B	117.9 (14)	C14A—C13A—H13A	119.3
C4B—C3B—H3BA	121.0	C12A—C13A—H13A	119.3
C2B—C3B—H3BA	121.0	C14B—C13B—C12B	122.6 (13)
N2—C3—C2	104.9 (14)	C14B—C13B—H13B	118.7
N2—C3—H3A	110.8	C12B—C13B—H13B	118.7
C2—C3—H3A	110.8	C13A—C14A—C5A	121.6 (13)
N2—C3—H3B	110.8	C13A—C14A—H14A	119.2
C2—C3—H3B	110.8	C5A—C14A—H14A	119.2
H3A—C3—H3B	108.9	C13B—C14B—C5B	122.4 (13)
C3A—C4A—C5A	120.0 (14)	C13B—C14B—H14B	118.8
C3A—C4A—H4AA	120.0	C5B—C14B—H14B	118.8
C5A—C4A—H4AA	120.0	O2—Cl1—O3	109.6 (7)
C3B—C4B—C5B	119.9 (13)	O2—Cl1—O1	109.6 (6)
C3B—C4B—H4BA	120.0	O3—Cl1—O1	109.5 (6)
C5B—C4B—H4BA	120.0	O2—Cl1—O4	109.9 (6)
N1—C4—H4A	109.5	O3—Cl1—O4	108.9 (6)
N1—C4—H4B	109.5	O1—Cl1—O4	109.4 (6)
H4A—C4—H4B	109.5	O8—Cl2—O6	110.6 (9)
N1—C4—H4C	109.5	O8—Cl2—O5	111.2 (7)
H4A—C4—H4C	109.5	O6—Cl2—O5	110.5 (7)
H4B—C4—H4C	109.5	O8—Cl2—O7	108.2 (8)
C4A—C5A—C14A	124.1 (13)	O6—Cl2—O7	107.9 (8)
C4A—C5A—C6A	116.8 (12)	O5—Cl2—O7	108.3 (7)
C5—N2—C1—N1	−174.7 (14)	C5A—C6A—C7A—N8A	−177.9 (13)
C3—N2—C1—N1	1.8 (18)	N1A—C6A—C7A—C12A	178.5 (13)
C5—N2—C1—Se1	3 (2)	C5A—C6A—C7A—C12A	2 (2)
C3—N2—C1—Se1	179.3 (12)	C9B—N8B—C7B—C6B	−179.1 (12)
C4—N1—C1—N2	−179.7 (15)	C9B—N8B—C7B—C12B	1 (2)
C2—N1—C1—N2	0.1 (18)	N1B—C6B—C7B—N8B	−0.7 (19)
C4—N1—C1—Se1	3 (2)	C5B—C6B—C7B—N8B	178.3 (12)
C2—N1—C1—Se1	−177.5 (11)	N1B—C6B—C7B—C12B	179.5 (12)
C6A—N1A—C2A—C3A	1 (2)	C5B—C6B—C7B—C12B	−1 (2)
C6B—N1B—C2B—C3B	−2 (2)	C7A—N8A—C9A—C10A	2 (2)
C1—N1—C2—C3	−1.9 (18)	C7B—N8B—C9B—C10B	0 (2)
C4—N1—C2—C3	177.9 (14)	N8A—C9A—C10A—C11A	−3 (2)
N1A—C2A—C3A—C4A	1 (2)	N8B—C9B—C10B—C11B	−2 (2)
N1B—C2B—C3B—C4B	1 (2)	C9A—C10A—C11A—C12A	0 (2)
C1—N2—C3—C2	−2.9 (19)	C9B—C10B—C11B—C12B	2 (2)
C5—N2—C3—C2	173.7 (14)	C10A—C11A—C12A—C7A	2 (2)
N1—C2—C3—N2	2.8 (18)	C10A—C11A—C12A—C13A	−177.7 (15)
C2A—C3A—C4A—C5A	0 (2)	N8A—C7A—C12A—C11A	−3 (2)
C2B—C3B—C4B—C5B	0 (2)	C6A—C7A—C12A—C11A	177.0 (14)
C3A—C4A—C5A—C14A	179.4 (13)	N8A—C7A—C12A—C13A	177.3 (13)
C3A—C4A—C5A—C6A	−2 (2)	C6A—C7A—C12A—C13A	−3 (2)
C3B—C4B—C5B—C6B	0 (2)	C10B—C11B—C12B—C7B	−1 (2)
C3B—C4B—C5B—C14B	179.5 (14)	C10B—C11B—C12B—C13B	176.5 (14)
C2A—N1A—C6A—C7A	−179.4 (13)	N8B—C7B—C12B—C11B	0 (2)
C2A—N1A—C6A—C5A	−3 (2)	C6B—C7B—C12B—C11B	179.4 (13)
C4A—C5A—C6A—N1A	4 (2)	N8B—C7B—C12B—C13B	−178.2 (12)
C14A—C5A—C6A—N1A	−177.7 (12)	C6B—C7B—C12B—C13B	1.6 (19)
C4A—C5A—C6A—C7A	−179.8 (13)	C11A—C12A—C13A—C14A	−176.9 (16)
C14A—C5A—C6A—C7A	−2 (2)	C7A—C12A—C13A—C14A	3 (2)
C2B—N1B—C6B—C7B	−178.2 (13)	C11B—C12B—C13B—C14B	−177.8 (15)
C2B—N1B—C6B—C5B	3 (2)	C7B—C12B—C13B—C14B	0 (2)
C4B—C5B—C6B—N1B	−2 (2)	C12A—C13A—C14A—C5A	−2 (2)
C14B—C5B—C6B—N1B	178.9 (13)	C4A—C5A—C14A—C13A	179.7 (14)
C4B—C5B—C6B—C7B	179.4 (12)	C6A—C5A—C14A—C13A	2 (2)
C14B—C5B—C6B—C7B	0 (2)	C12B—C13B—C14B—C5B	−1 (2)
C9A—N8A—C7A—C12A	0 (2)	C4B—C5B—C14B—C13B	−177.9 (14)
C9A—N8A—C7A—C6A	−179.4 (13)	C6B—C5B—C14B—C13B	2 (2)
N1A—C6A—C7A—N8A	−1.6 (18)

(II) bis(2,2'-bipyridyl-κ²N,N')(imidazolidine-2-thione- κS)copper(II) bis(perchlorate)

Crystal data

[Cu(C10H8N2)2(C3H6N2S)](ClO4)2	F(000) = 1380
Mr = 676.97	Dx = 1.636 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 58 reflections
a = 11.493 (7) Å	θ = 12.5–14.5°
b = 11.861 (9) Å	µ = 1.12 mm^−1
c = 20.166 (10) Å	T = 150 K
V = 2749 (3) Å^3	Ingot, green
Z = 4	0.54 × 0.27 × 0.18 mm

Data collection

Stoe Stadi-4 four-circle diffractometer	3420 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
Graphite monochromator	θmax = 25.1°, θmin = 2.7°
ω/θ scans	h = −6→13
Absorption correction: numerical (X-RED; Stoe & Cie, 1996)	k = 0→14
Tmin = 0.747, Tmax = 0.840	l = 0→23
4959 measured reflections	3 standard reflections every 60 min
3932 independent reflections	intensity decay: random variation +/−6%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: included in calculated positions; except for N-H (found in delta-F)
R[F^2 > 2σ(F^2)] = 0.061	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.164	w = 1/[σ^2(Fo^2) + (0.084P)^2 + 11.27P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.004
3932 reflections	Δρmax = 1.18 e Å^−3
377 parameters	Δρmin = −0.56 e Å^−3
2 restraints	Absolute structure: Flack (1983), 1186 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (3)

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

	x	y	z	Uiso*/Ueq
Cu1	0.96775 (8)	0.91289 (8)	0.24280 (4)	0.0358 (3)
S1	0.9224 (2)	0.72098 (16)	0.22395 (10)	0.0407 (6)
N1	0.7710 (7)	0.6768 (6)	0.1268 (3)	0.042 (2)
N1A	0.8532 (6)	1.0305 (5)	0.2796 (3)	0.0323 (17)
N1B	1.0403 (6)	0.8705 (5)	0.3285 (3)	0.0353 (19)
N2	0.6996 (7)	0.7828 (6)	0.2041 (3)	0.041 (2)
N8A	0.8936 (6)	0.9646 (5)	0.1587 (3)	0.0343 (19)
N8B	1.1380 (6)	0.9586 (5)	0.2231 (3)	0.036 (2)
C1	0.7915 (8)	0.7291 (7)	0.1835 (4)	0.036 (3)
C2	0.6538 (10)	0.7063 (8)	0.1005 (4)	0.054 (3)
C2A	0.8478 (8)	1.0708 (7)	0.3423 (4)	0.039 (3)
C2B	0.9823 (9)	0.8208 (7)	0.3791 (4)	0.047 (3)
C3	0.5977 (9)	0.7619 (8)	0.1612 (5)	0.052 (3)
C3A	0.7747 (8)	1.1572 (7)	0.3604 (4)	0.038 (3)
C3B	1.0354 (9)	0.7944 (7)	0.4378 (4)	0.047 (3)
C4A	0.7084 (8)	1.2078 (7)	0.3130 (4)	0.044 (3)
C4B	1.1526 (10)	0.8186 (8)	0.4450 (5)	0.056 (3)
C5A	0.7131 (7)	1.1672 (6)	0.2484 (4)	0.037 (2)
C5B	1.2121 (8)	0.8678 (7)	0.3934 (4)	0.042 (3)
C6A	0.7867 (6)	1.0798 (6)	0.2331 (3)	0.031 (2)
C6B	1.1541 (7)	0.8941 (6)	0.3355 (4)	0.035 (2)
C7A	0.8058 (7)	1.0353 (6)	0.1650 (4)	0.033 (2)
C7B	1.2099 (8)	0.9447 (6)	0.2759 (4)	0.037 (3)
C9A	0.9182 (8)	0.9202 (7)	0.0986 (4)	0.042 (3)
C9B	1.1809 (9)	1.0071 (7)	0.1683 (4)	0.044 (3)
C10A	0.8531 (9)	0.9482 (7)	0.0432 (4)	0.046 (3)
C10B	1.2963 (8)	1.0428 (8)	0.1638 (5)	0.047 (3)
C11A	0.7601 (9)	1.0201 (7)	0.0495 (4)	0.048 (3)
C11B	1.3678 (9)	1.0253 (8)	0.2169 (5)	0.054 (3)
C12A	0.7347 (8)	1.0636 (6)	0.1114 (4)	0.040 (3)
C12B	1.3261 (8)	0.9759 (7)	0.2738 (4)	0.043 (3)
H1	0.840 (4)	0.654 (7)	0.111 (4)	0.0500*
H5AA	0.66560	1.19980	0.21490	0.0450*
H2	0.699 (8)	0.807 (7)	0.2465 (17)	0.0490*
H4AA	0.65970	1.26980	0.32390	0.0520*
H2B	0.61040	0.63830	0.08650	0.0650*
H2C	0.65920	0.75950	0.06280	0.0650*
H3AA	0.77040	1.18120	0.40520	0.0460*
H3A	0.55810	0.83320	0.14920	0.0620*
H3B	0.54120	0.71080	0.18290	0.0620*
H2AA	0.89650	1.03810	0.37520	0.0470*
H9AA	0.98130	0.86900	0.09430	0.0500*
H5BA	1.29280	0.88360	0.39760	0.0510*
H4BA	1.19150	0.80130	0.48520	0.0680*
H3BA	0.99290	0.76020	0.47280	0.0570*
H2BA	0.90210	0.80380	0.37360	0.0570*
H9BA	1.13110	1.01750	0.13120	0.0520*
H10A	0.87270	0.91780	0.00100	0.0550*
H10B	1.32450	1.07840	0.12470	0.0560*
H11A	0.71410	1.03960	0.01210	0.0580*
H11B	1.44710	1.04740	0.21450	0.0650*
H12A	0.66970	1.11200	0.11740	0.0480*
H12B	1.37570	0.96340	0.31080	0.0520*
Cl1	0.92029 (19)	0.60874 (17)	−0.01995 (8)	0.0404 (6)
O1	0.9866 (6)	0.5334 (5)	−0.0602 (3)	0.053 (2)
O2	0.9693 (7)	0.6148 (8)	0.0446 (3)	0.084 (3)
O3	0.8035 (7)	0.5678 (8)	−0.0143 (4)	0.079 (3)
O4	0.9191 (7)	0.7161 (6)	−0.0490 (4)	0.071 (3)
Cl2	0.57729 (18)	0.85245 (17)	0.37624 (9)	0.0366 (6)
O5	0.6038 (7)	0.9054 (7)	0.3145 (3)	0.076 (3)
O6	0.5155 (7)	0.9312 (7)	0.4150 (3)	0.081 (3)
O7	0.5067 (7)	0.7602 (7)	0.3633 (5)	0.088 (4)
O8	0.6832 (6)	0.8203 (7)	0.4081 (4)	0.070 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0329 (5)	0.0419 (5)	0.0327 (4)	0.0017 (5)	0.0028 (4)	0.0067 (4)
S1	0.0391 (11)	0.0356 (9)	0.0474 (11)	0.0044 (10)	0.0002 (10)	0.0068 (8)
N1	0.049 (5)	0.044 (4)	0.032 (3)	−0.004 (4)	0.003 (3)	0.000 (3)
N1A	0.024 (3)	0.040 (3)	0.033 (3)	−0.001 (3)	0.001 (3)	0.005 (3)
N1B	0.039 (4)	0.031 (3)	0.036 (3)	0.000 (3)	0.004 (3)	0.001 (3)
N2	0.035 (4)	0.052 (4)	0.036 (3)	−0.001 (4)	0.003 (3)	−0.003 (3)
N8A	0.040 (4)	0.031 (3)	0.032 (3)	0.000 (3)	0.004 (3)	0.006 (3)
N8B	0.035 (4)	0.031 (3)	0.042 (4)	0.001 (3)	0.007 (3)	−0.007 (3)
C1	0.038 (5)	0.037 (4)	0.034 (4)	−0.001 (4)	0.005 (4)	0.009 (3)
C2	0.064 (7)	0.058 (5)	0.041 (5)	−0.003 (5)	−0.009 (5)	0.001 (4)
C2A	0.038 (5)	0.049 (5)	0.030 (4)	−0.003 (4)	−0.005 (4)	0.000 (3)
C2B	0.047 (6)	0.050 (5)	0.045 (5)	0.006 (5)	−0.003 (5)	0.011 (4)
C3	0.049 (6)	0.055 (5)	0.051 (5)	0.005 (5)	0.001 (5)	0.009 (4)
C3A	0.033 (5)	0.046 (5)	0.036 (4)	−0.008 (4)	0.004 (4)	−0.001 (3)
C3B	0.050 (6)	0.056 (5)	0.035 (4)	0.008 (5)	0.007 (4)	0.017 (4)
C4A	0.041 (5)	0.038 (4)	0.052 (5)	−0.001 (4)	0.015 (4)	0.000 (4)
C4B	0.063 (7)	0.057 (6)	0.049 (5)	0.012 (6)	−0.004 (5)	0.007 (4)
C5A	0.031 (4)	0.041 (4)	0.039 (4)	−0.002 (4)	0.002 (4)	0.017 (4)
C5B	0.037 (5)	0.051 (5)	0.039 (4)	0.008 (4)	−0.001 (4)	−0.002 (4)
C6A	0.028 (4)	0.034 (4)	0.031 (3)	−0.011 (4)	0.004 (3)	0.006 (3)
C6B	0.035 (4)	0.035 (4)	0.035 (4)	0.011 (4)	0.002 (3)	−0.004 (3)
C7A	0.035 (5)	0.022 (3)	0.042 (4)	−0.006 (4)	−0.007 (4)	0.011 (3)
C7B	0.036 (5)	0.030 (4)	0.044 (4)	0.002 (4)	0.002 (4)	0.001 (3)
C9A	0.047 (5)	0.041 (4)	0.038 (4)	−0.010 (5)	0.010 (4)	0.000 (3)
C9B	0.049 (6)	0.043 (4)	0.039 (4)	0.003 (4)	0.008 (4)	0.006 (4)
C10A	0.059 (6)	0.041 (4)	0.037 (4)	−0.012 (5)	0.012 (4)	0.004 (3)
C10B	0.043 (5)	0.051 (5)	0.047 (5)	−0.011 (5)	0.020 (5)	−0.004 (4)
C11A	0.055 (6)	0.047 (5)	0.043 (5)	−0.018 (5)	−0.005 (4)	0.008 (4)
C11B	0.043 (5)	0.052 (5)	0.066 (6)	−0.006 (5)	0.017 (5)	−0.025 (5)
C12A	0.042 (5)	0.036 (4)	0.042 (4)	−0.007 (4)	−0.005 (4)	0.011 (3)
C12B	0.039 (5)	0.039 (4)	0.051 (5)	−0.003 (4)	−0.002 (4)	−0.006 (4)
Cl1	0.0430 (11)	0.0530 (11)	0.0251 (8)	0.0040 (10)	−0.0003 (8)	0.0021 (8)
O1	0.050 (4)	0.060 (4)	0.049 (3)	0.000 (4)	0.003 (3)	−0.011 (3)
O2	0.075 (5)	0.149 (7)	0.029 (3)	0.040 (6)	−0.019 (3)	−0.016 (4)
O3	0.058 (5)	0.113 (6)	0.066 (4)	−0.017 (5)	0.016 (4)	−0.018 (4)
O4	0.071 (5)	0.074 (4)	0.068 (4)	0.023 (4)	0.019 (4)	0.024 (4)
Cl2	0.0304 (10)	0.0500 (11)	0.0293 (8)	0.0011 (10)	−0.0002 (8)	−0.0026 (8)
O5	0.078 (5)	0.097 (5)	0.053 (4)	0.014 (5)	0.021 (4)	0.022 (4)
O6	0.068 (5)	0.109 (6)	0.066 (4)	0.031 (5)	−0.010 (4)	−0.052 (4)
O7	0.044 (5)	0.069 (5)	0.151 (8)	−0.009 (4)	−0.003 (5)	−0.007 (5)
O8	0.046 (4)	0.099 (6)	0.064 (4)	0.014 (4)	−0.013 (4)	0.008 (4)

Geometric parameters (Å, º)

Cu1—S1	2.366 (3)	C4B—C5B	1.375 (13)
Cu1—N1A	2.057 (7)	C5A—C6A	1.373 (10)
Cu1—N1B	1.984 (6)	C5B—C6B	1.380 (12)
Cu1—N8A	1.995 (6)	C6A—C7A	1.488 (10)
Cu1—N8B	2.069 (7)	C6B—C7B	1.489 (11)
Cl1—O1	1.428 (7)	C7A—C12A	1.396 (12)
Cl1—O2	1.420 (7)	C7B—C12B	1.387 (13)
Cl1—O3	1.432 (9)	C9A—C10A	1.385 (12)
Cl1—O4	1.402 (7)	C9B—C10B	1.395 (14)
Cl2—O5	1.427 (7)	C10A—C11A	1.373 (14)
Cl2—O6	1.410 (8)	C10B—C11B	1.366 (14)
Cl2—O7	1.387 (9)	C11A—C12A	1.382 (12)
Cl2—O8	1.428 (8)	C11B—C12B	1.375 (13)
S1—C1	1.714 (9)	C2—H2B	0.9900
N1—C2	1.489 (14)	C2—H2C	0.9900
N1—C1	1.322 (10)	C2A—H2AA	0.9500
N1A—C2A	1.353 (10)	C2B—H2BA	0.9500
N1A—C6A	1.344 (9)	C3—H3A	0.9900
N1B—C6B	1.345 (11)	C3—H3B	0.9900
N1B—C2B	1.354 (11)	C3A—H3AA	0.9500
N2—C1	1.302 (12)	C3B—H3BA	0.9500
N2—C3	1.477 (13)	C4A—H4AA	0.9500
N8A—C7A	1.318 (10)	C4B—H4BA	0.9500
N8A—C9A	1.351 (10)	C5A—H5AA	0.9500
N8B—C7B	1.358 (11)	C5B—H5BA	0.9500
N8B—C9B	1.340 (11)	C9A—H9AA	0.9500
N1—H1	0.90 (5)	C9B—H9BA	0.9500
N2—H2	0.90 (4)	C10A—H10A	0.9500
C2—C3	1.533 (14)	C10B—H10B	0.9500
C2A—C3A	1.375 (12)	C11A—H11A	0.9500
C2B—C3B	1.368 (12)	C11B—H11B	0.9500
C3A—C4A	1.362 (12)	C12A—H12A	0.9500
C3B—C4B	1.385 (15)	C12B—H12B	0.9500
C4A—C5A	1.390 (11)
S1—Cu1—N1A	124.72 (19)	C5B—C6B—C7B	124.5 (8)
S1—Cu1—N1B	89.35 (18)	N1B—C6B—C5B	120.8 (7)
S1—Cu1—N8A	93.73 (18)	C6A—C7A—C12A	122.9 (7)
S1—Cu1—N8B	115.44 (18)	N8A—C7A—C12A	121.8 (7)
N1A—Cu1—N1B	97.3 (3)	N8A—C7A—C6A	115.3 (7)
N1A—Cu1—N8A	79.9 (3)	N8B—C7B—C6B	114.8 (7)
N1A—Cu1—N8B	119.8 (2)	C6B—C7B—C12B	123.2 (7)
N1B—Cu1—N8A	176.7 (2)	N8B—C7B—C12B	122.0 (7)
N1B—Cu1—N8B	80.6 (3)	N8A—C9A—C10A	121.1 (8)
N8A—Cu1—N8B	99.2 (3)	N8B—C9B—C10B	122.3 (8)
O1—Cl1—O2	109.9 (5)	C9A—C10A—C11A	119.7 (8)
O1—Cl1—O3	109.5 (5)	C9B—C10B—C11B	118.4 (9)
O1—Cl1—O4	109.7 (4)	C10A—C11A—C12A	118.7 (8)
O2—Cl1—O3	108.4 (5)	C10B—C11B—C12B	120.6 (9)
O2—Cl1—O4	109.9 (5)	C7A—C12A—C11A	119.1 (8)
O3—Cl1—O4	109.4 (5)	C7B—C12B—C11B	118.4 (8)
O5—Cl2—O6	107.4 (5)	N1—C2—H2C	112.00
O5—Cl2—O7	107.9 (5)	C3—C2—H2B	112.00
O5—Cl2—O8	109.1 (5)	N1—C2—H2B	111.00
O6—Cl2—O7	109.4 (5)	C3—C2—H2C	111.00
O6—Cl2—O8	110.9 (5)	H2B—C2—H2C	109.00
O7—Cl2—O8	111.9 (5)	N1A—C2A—H2AA	119.00
Cu1—S1—C1	102.5 (3)	C3A—C2A—H2AA	119.00
C1—N1—C2	111.0 (7)	N1B—C2B—H2BA	119.00
Cu1—N1A—C6A	114.1 (5)	C3B—C2B—H2BA	119.00
Cu1—N1A—C2A	127.3 (6)	N2—C3—H3B	111.00
C2A—N1A—C6A	118.2 (7)	N2—C3—H3A	111.00
Cu1—N1B—C2B	124.1 (6)	H3A—C3—H3B	109.00
Cu1—N1B—C6B	116.6 (5)	C2—C3—H3A	111.00
C2B—N1B—C6B	119.4 (7)	C2—C3—H3B	111.00
C1—N2—C3	112.0 (7)	C2A—C3A—H3AA	121.00
C7A—N8A—C9A	119.6 (7)	C4A—C3A—H3AA	120.00
Cu1—N8A—C7A	116.2 (5)	C2B—C3B—H3BA	121.00
Cu1—N8A—C9A	123.6 (5)	C4B—C3B—H3BA	121.00
C7B—N8B—C9B	118.4 (7)	C3A—C4A—H4AA	121.00
Cu1—N8B—C9B	128.2 (6)	C5A—C4A—H4AA	121.00
Cu1—N8B—C7B	113.2 (5)	C5B—C4B—H4BA	120.00
C1—N1—H1	107 (5)	C3B—C4B—H4BA	120.00
C2—N1—H1	138 (5)	C4A—C5A—H5AA	120.00
C3—N2—H2	127 (6)	C6A—C5A—H5AA	120.00
C1—N2—H2	118 (6)	C6B—C5B—H5BA	120.00
S1—C1—N1	122.8 (7)	C4B—C5B—H5BA	120.00
N1—C1—N2	111.2 (8)	N8A—C9A—H9AA	119.00
S1—C1—N2	126.0 (6)	C10A—C9A—H9AA	119.00
N1—C2—C3	101.4 (7)	N8B—C9B—H9BA	119.00
N1A—C2A—C3A	122.7 (8)	C10B—C9B—H9BA	119.00
N1B—C2B—C3B	122.2 (9)	C11A—C10A—H10A	120.00
N2—C3—C2	101.9 (8)	C9A—C10A—H10A	120.00
C2A—C3A—C4A	119.0 (8)	C9B—C10B—H10B	121.00
C2B—C3B—C4B	118.5 (9)	C11B—C10B—H10B	121.00
C3A—C4A—C5A	118.9 (8)	C10A—C11A—H11A	121.00
C3B—C4B—C5B	119.5 (9)	C12A—C11A—H11A	121.00
C4A—C5A—C6A	119.7 (7)	C10B—C11B—H11B	120.00
C4B—C5B—C6B	119.7 (9)	C12B—C11B—H11B	120.00
N1A—C6A—C7A	114.0 (6)	C7A—C12A—H12A	120.00
C5A—C6A—C7A	124.5 (6)	C11A—C12A—H12A	120.00
N1A—C6A—C5A	121.5 (6)	C11B—C12B—H12B	121.00
N1B—C6B—C7B	114.7 (7)	C7B—C12B—H12B	121.00
C2—N1—C1—S1	−175.4 (6)	C3B—C4B—C5B—C6B	1.0 (13)
C2—N1—C1—N2	6.4 (10)	C4A—C5A—C6A—C7A	−175.1 (7)
C1—N1—C2—C3	−13.8 (9)	C4A—C5A—C6A—N1A	1.4 (11)
C6A—N1A—C2A—C3A	2.1 (12)	C4B—C5B—C6B—N1B	−1.1 (12)
C2A—N1A—C6A—C5A	−1.3 (11)	C4B—C5B—C6B—C7B	−178.4 (8)
C2A—N1A—C6A—C7A	175.5 (7)	N1A—C6A—C7A—C12A	170.8 (7)
C6B—N1B—C2B—C3B	0.6 (12)	N1A—C6A—C7A—N8A	−7.7 (10)
C2B—N1B—C6B—C5B	0.3 (11)	C5A—C6A—C7A—C12A	−12.5 (12)
C2B—N1B—C6B—C7B	177.8 (7)	C5A—C6A—C7A—N8A	169.0 (7)
C3—N2—C1—S1	−173.4 (7)	N1B—C6B—C7B—N8B	−0.6 (9)
C3—N2—C1—N1	4.7 (10)	C5B—C6B—C7B—C12B	−3.3 (12)
C1—N2—C3—C2	−13.0 (9)	N1B—C6B—C7B—C12B	179.3 (7)
C9A—N8A—C7A—C6A	−179.6 (7)	C5B—C6B—C7B—N8B	176.9 (7)
C9A—N8A—C7A—C12A	1.9 (11)	N8A—C7A—C12A—C11A	−2.8 (12)
C7A—N8A—C9A—C10A	0.4 (12)	C6A—C7A—C12A—C11A	178.8 (7)
C9B—N8B—C7B—C6B	177.8 (7)	N8B—C7B—C12B—C11B	1.9 (12)
C9B—N8B—C7B—C12B	−2.0 (11)	C6B—C7B—C12B—C11B	−177.9 (8)
C7B—N8B—C9B—C10B	0.4 (12)	N8A—C9A—C10A—C11A	−1.6 (13)
N1—C2—C3—N2	14.9 (8)	N8B—C9B—C10B—C11B	1.3 (14)
N1A—C2A—C3A—C4A	−2.9 (13)	C9A—C10A—C11A—C12A	0.6 (13)
N1B—C2B—C3B—C4B	−0.7 (13)	C9B—C10B—C11B—C12B	−1.4 (14)
C2A—C3A—C4A—C5A	2.8 (13)	C10A—C11A—C12A—C7A	1.5 (13)
C2B—C3B—C4B—C5B	−0.2 (13)	C10B—C11B—C12B—C7B	−0.2 (13)
C3A—C4A—C5A—C6A	−2.1 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.90 (5)	2.05 (7)	2.913 (11)	160 (7)
N2—H2···O5	0.90 (4)	2.11 (7)	2.878 (10)	143 (7)