catena-Poly[[[bis([mu]-4,5-dihydrothiazole-2-thiolato)-tetrahedro-tetracopper(I)]-di-[mu]-4,5-dihydrothiazole-2-thiolato] dihydrate]

The title compound, {[Cu₄(C₃H₄NS₂)₄]·2H₂O}_n, was produced by diffusing a solution of 2-mercapto­thia­zoline in tetra­hydro­furan into a solution of CuCl in CH₃CN at room temperature. The structure is characterized by self-assembled one-dimensional chains that are condensed from butterfly-like [Cu(C₃H₄NS₂)]₄ tetrameric units via double S-bridging at opposite ends. The Cu-Cu distances within the Cu₄ butterfly cluster are in the range 2.7103 (10)-2.9764 (10) Å, while the shortest Cu...Cu intercluster distance is 3.468 (1) Å, much longer than the sum of the van der Waals radii.

S1. Comment

Polynuclear d¹⁰ metal complexes are potential luminescent sensor materials due to their interesting photochemical and photophysical properties (Ford et al., 1999; Yam & Lo, 1999). In a recent effort to investigate the dependence of the optical properties of coinage metal complexes on molecular structure and metal-metal interactions (Zhou et al., 2002), a variety of novel polynuclear compounds have been obtained through the selective use of different chelating ligands. Copper complexes with 2-mercaptothiazoline (or 2-thiazolidine-2-thione) ligands have been reported previously, e.g. for mononuclear [Cu(C₃H₅NS₂)₃Cl] (Zhao et al., 1985) and [(PPh₃)₂Cu(C₃H₄NS₂)] (Aslanidis et al., 1998), as well as for polymeric [Cu(C₃H₄NS₂)]₄·C₇H₈, which was prepared electrochemically (Raper et al., 1995). In this paper, we report the solution synthesis and single-crystal structure of the title compound, (I), which features similar tetracopper(I) chain structures but with different dimensions, due to solvation effects. \sch

The marked structural feature of (I) is the formation of one-dimensional chains that are built up from butterfly-like [Cu(C₃H₄NS₂)]₄ tetrameric units. As shown in Fig. 1, each building block consists of four Cu atoms divided into two categories, with Cu1 and Cu2 in a distorted S₃N tetrahedral coordination geometry, and Cu3 and Cu4 in a distorted S₂N triangle. The distance between atoms Cu1 and Cu2 on the `wing-tip' [3.775 (1) Å] is much longer than that between the `spinal' atoms Cu3 and Cu4 [2.9764 (10) Å], yielding a butterfly-like shape.

These butterfly-like tetramers link with neighbouring units through the wing-tip atoms Cu1 and Cu2 via S bridging atoms (S21 and S11) at opposite ends, leading to an infinite one-dimensional structure along the [110] direction (Fig. 2). The chain extension at both ends is actually generated through centrosymmetrically related Cu₂S₂ motifs. The intra-tetramer Cu—Cu distances are in the range 2.7103 (10)–2.9764 (10) Å, slightly longer than the range of 2.692 (4)–2.882 (5) Å reported in [Cu(C₃H₄NS₂)]₄·C₇H₈ (Raper et al., 1995).

The intercluster distances of 3.468 (1) Å for Cu1—Cu1ⁱ and 3.487 (1) Å for Cu2—Cu2ⁱⁱ (Fig. 1) [symmetry codes: (i) 1 - x, 1 - y, -z; (ii) -x, 2 - y, -z Are these the correct symmetry codes?], are significantly longer in comparison with the intracluster distances, and are well above the sum of the van der Waals radii, implying no direct metal-metal interaction between tetramers. It is worth noting that the Cu—Cu distances around atom Cu3 are slightly longer than those around atom Cu4, presumably because 2-mercaptothiazoline is a very asymmetric bidendate ligand. Uncoordinated water molecules are located between the polymeric chains to serve for efficient solvation and packing.

While each C₃H₄NS₂ moiety serves as a bidendate ligand through the N and thionato S atoms, the four ligands around the tetrameric Cu^I unit are grouped into two types in accordance with the butterfly-like configuration. Ligands 3 and 4 are coordinated to only one tetramer, whereas ligands 1 and 2 play additional roles to bridge two neighbouring tetramers via the thionato S atoms. The bond distances associated with the centrosymmetrically related Cu₂S₂ units are Cu1—S21 2.4393 (14) and 2.6702 (14) Å, and Cu2—S11 2.4463 (14) and 2.5880 (14) Å, which are slightly shorter than those in [Cu(C₃H₄NS₂)]₄·C₇H₈ [2.539 (3) and 2.790 (3) Å], presumably due to the presence of the water solvent molecules, which are smaller than the toluene. The remaining Cu—S distances are in the range 2.2191 (13)–2.3163 (14) Å, with Cu—N distances ranging from 1.991 (4) to 2.021 (4) Å; both are in good agreement with those reported in [Cu(C₃H₄NS₂)]₄·C₇H₈ (Raper et al., 1995) and [Cu(1-methylimidazoline-2(3H)-thionate)]₄ (Raper et al., 1991).

S2. Experimental

Block-like pale-yellow crystals of (I) were obtained by diffusing a solution of 2-mercaptothiazoline (0.160 g) in tetrahydrofuran (6 ml) into a solution of CuCl (0.033 g) in CH₃CN (6 ml) at room temperature for four weeks.

S3. Refinement

The H atoms on the ligands were located at geometrically calculated positions with H-atom parameters constrained (C—H = 0.97 Å). The aqua H atoms were not located in the structure. The highest residual peak (1.60 e Å^-3) is located at the position (0.142, 0.816, 0.460), which is 0.59 Å from O (which O atom?); the deepest hole (-0.67 e Å^-3) is located at the position (0.185, 0.582, 0.070), which is 0.80 Å from Cu.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: XCAD4 (Harms, 1996); data reduction: XCAD4; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The tetrameric Cu^I building blocks in polymeric (I). Displacement ellipsoids are drawn at the 50% probability level, and H atoms and the hydrate water molecules have been omitted for clarity [symmetry codes: (i) 1 - x, 1 - y, -z; (ii) -x, 2 - y, -z].
	Fig. 2. The one-dimensional chain in the polymer of (I). H and O atoms have been omitted for clarity and displacement ellipsoids are drawn at the 30% probability level.

catena-Poly[[[bis(µ-4,5-dihydrothiazole-2-thiolato)-tetrahedro-tetracopper(I)]- di-µ-4,5-dihydrothiazole-2-thiolato] dihydrate]

Crystal data

[Cu4(C3H4NS2)4]·2H2O	Z = 2
Mr = 763.08	F(000) = 760
Triclinic, P1	Dx = 2.059 Mg m^−3
a = 9.8888 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.7259 (10) Å	Cell parameters from 25 reflections
c = 13.1808 (10) Å	θ = 1–26°
α = 69.45 (1)°	µ = 4.11 mm^−1
β = 82.737 (10)°	T = 293 K
γ = 70.075 (10)°	Block, yellow
V = 1230.67 (19) Å^3	0.32 × 0.30 × 0.30 mm

Data collection

Query diffractometer	4777 independent reflections
Radiation source: fine-focus sealed tube	4208 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
Detector resolution: none pixels mm^-1	θmax = 26.0°, θmin = 2.2°
ω/2θ scans	h = 0→12
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −12→13
Tmin = 0.287, Tmax = 0.292	l = −16→16
5061 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.170	H-atom parameters constrained
S = 0.88	w = 1/[σ^2(Fo^2) + (0.1535P)^2 + 1.4219P] where P = (Fo^2 + 2Fc^2)/3
4777 reflections	(Δ/σ)max = 0.001
272 parameters	Δρmax = 1.60 e Å^−3
0 restraints	Δρmin = −0.67 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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.40027 (8)	0.58871 (7)	0.08625 (6)	0.0443 (2)
Cu2	0.03274 (7)	0.83752 (7)	−0.01586 (5)	0.0385 (2)
Cu3	0.15483 (7)	0.53354 (7)	0.05125 (5)	0.0388 (2)
Cu4	0.15312 (6)	0.70915 (6)	0.18339 (5)	0.0322 (2)
S11	0.16403 (12)	0.91962 (11)	0.07883 (10)	0.0296 (3)
S12	0.35015 (14)	1.04639 (13)	−0.09779 (12)	0.0417 (3)
S21	0.32517 (12)	0.56377 (11)	−0.07297 (9)	0.0275 (3)
S22	0.34792 (17)	0.77038 (15)	−0.29250 (11)	0.0477 (4)
S31	−0.08035 (12)	0.67158 (12)	0.04980 (9)	0.0297 (3)
S32	−0.24033 (16)	0.57429 (17)	0.25791 (12)	0.0453 (4)
S41	0.33675 (13)	0.50400 (12)	0.26153 (10)	0.0340 (3)
S42	0.2492 (2)	0.25320 (16)	0.39916 (11)	0.0533 (4)
O1	−0.5545 (5)	0.8390 (6)	0.4233 (3)	0.0653 (14)
O2	−0.1788 (4)	1.2147 (4)	−0.4323 (4)	0.0476 (10)
N1	0.4213 (4)	0.7789 (4)	0.0122 (3)	0.0279 (8)
N2	0.1495 (4)	0.8335 (4)	−0.1528 (3)	0.0296 (8)
N3	−0.0275 (4)	0.6690 (4)	0.2459 (3)	0.0301 (8)
N4	0.1846 (4)	0.3809 (4)	0.1954 (3)	0.0311 (8)
C11	0.3235 (5)	0.8964 (5)	0.0026 (4)	0.0268 (9)
C12	0.5160 (6)	0.9403 (5)	−0.1417 (5)	0.0403 (12)
H12A	0.5073	0.9441	−0.2153	0.048*
H12B	0.5948	0.9736	−0.1392	0.048*
C13	0.5429 (5)	0.7883 (5)	−0.0624 (4)	0.0351 (11)
H13A	0.5572	0.7250	−0.1032	0.042*
H13B	0.6296	0.7594	−0.0215	0.042*
C21	0.1163 (6)	0.9622 (5)	−0.2467 (4)	0.0391 (11)
H21A	0.1173	1.0398	−0.2255	0.047*
H21B	0.0206	0.9835	−0.2723	0.047*
C22	0.2233 (8)	0.9467 (7)	−0.3364 (5)	0.066 (2)
H22A	0.2743	1.0144	−0.3522	0.079*
H22B	0.1746	0.9632	−0.4015	0.079*
C23	0.2584 (5)	0.7337 (4)	−0.1666 (4)	0.0255 (9)
C31	−0.1041 (5)	0.6436 (5)	0.1888 (4)	0.0292 (9)
C32	−0.2003 (11)	0.5979 (15)	0.3781 (6)	0.100 (4)
H32A	−0.2776	0.6737	0.3936	0.120*
H32B	−0.1905	0.5126	0.4395	0.120*
C33	−0.0692 (7)	0.6305 (7)	0.3602 (5)	0.0467 (13)
H33A	0.0067	0.5497	0.4016	0.056*
H33B	−0.0801	0.7076	0.3860	0.056*
C41	0.2502 (5)	0.3833 (5)	0.2718 (4)	0.0303 (10)
C42	0.1206 (6)	0.2692 (6)	0.2286 (4)	0.0401 (11)
H42A	0.1699	0.2011	0.1925	0.048*
H42B	0.0204	0.3080	0.2071	0.048*
C43	0.1303 (12)	0.1979 (9)	0.3485 (6)	0.077 (3)
H43A	0.1659	0.0968	0.3652	0.093*
H43B	0.0359	0.2228	0.3816	0.093*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0570 (5)	0.0301 (4)	0.0443 (4)	−0.0191 (3)	0.0131 (3)	−0.0100 (3)
Cu2	0.0435 (4)	0.0421 (4)	0.0310 (4)	−0.0195 (3)	0.0090 (3)	−0.0108 (3)
Cu3	0.0369 (4)	0.0362 (4)	0.0290 (4)	−0.0051 (3)	0.0055 (3)	−0.0024 (3)
Cu4	0.0321 (3)	0.0307 (3)	0.0339 (4)	−0.0122 (2)	0.0044 (2)	−0.0102 (3)
S11	0.0255 (5)	0.0252 (5)	0.0361 (6)	−0.0064 (4)	0.0050 (4)	−0.0109 (5)
S12	0.0352 (7)	0.0250 (6)	0.0524 (8)	−0.0067 (5)	0.0096 (6)	−0.0044 (5)
S21	0.0300 (6)	0.0225 (5)	0.0264 (6)	−0.0061 (4)	0.0032 (4)	−0.0070 (4)
S22	0.0520 (8)	0.0389 (7)	0.0300 (7)	−0.0010 (6)	0.0136 (6)	−0.0029 (5)
S31	0.0282 (6)	0.0316 (6)	0.0267 (6)	−0.0090 (5)	0.0011 (4)	−0.0073 (5)
S32	0.0471 (8)	0.0612 (9)	0.0383 (7)	−0.0341 (7)	0.0122 (6)	−0.0170 (6)
S41	0.0317 (6)	0.0314 (6)	0.0353 (7)	−0.0079 (5)	−0.0005 (5)	−0.0087 (5)
S42	0.0799 (11)	0.0517 (9)	0.0268 (7)	−0.0334 (8)	−0.0073 (7)	0.0031 (6)
O1	0.068 (3)	0.119 (4)	0.031 (2)	−0.068 (3)	0.012 (2)	−0.019 (2)
O2	0.049 (2)	0.045 (2)	0.053 (2)	−0.0259 (18)	−0.0185 (18)	−0.0049 (18)
N1	0.0269 (18)	0.0264 (18)	0.032 (2)	−0.0108 (15)	0.0029 (15)	−0.0110 (16)
N2	0.032 (2)	0.0270 (19)	0.0251 (19)	−0.0082 (16)	0.0004 (15)	−0.0039 (15)
N3	0.0289 (19)	0.034 (2)	0.0262 (19)	−0.0099 (16)	0.0026 (15)	−0.0093 (16)
N4	0.0297 (19)	0.0280 (19)	0.029 (2)	−0.0082 (16)	0.0026 (16)	−0.0035 (16)
C11	0.025 (2)	0.026 (2)	0.031 (2)	−0.0099 (17)	0.0004 (17)	−0.0105 (18)
C12	0.038 (3)	0.035 (3)	0.045 (3)	−0.013 (2)	0.013 (2)	−0.012 (2)
C13	0.023 (2)	0.033 (2)	0.047 (3)	−0.0071 (19)	0.009 (2)	−0.015 (2)
C21	0.042 (3)	0.029 (2)	0.034 (3)	−0.006 (2)	0.000 (2)	0.000 (2)
C22	0.074 (4)	0.040 (3)	0.041 (3)	0.008 (3)	0.020 (3)	0.007 (3)
C23	0.030 (2)	0.023 (2)	0.023 (2)	−0.0102 (17)	0.0009 (17)	−0.0060 (17)
C31	0.030 (2)	0.023 (2)	0.029 (2)	−0.0070 (17)	0.0027 (18)	−0.0049 (18)
C32	0.105 (7)	0.207 (12)	0.042 (4)	−0.113 (8)	0.035 (4)	−0.055 (6)
C33	0.057 (3)	0.059 (3)	0.031 (3)	−0.029 (3)	0.006 (2)	−0.015 (2)
C41	0.030 (2)	0.023 (2)	0.027 (2)	−0.0006 (18)	0.0001 (18)	−0.0042 (18)
C42	0.048 (3)	0.038 (3)	0.036 (3)	−0.019 (2)	0.002 (2)	−0.011 (2)
C43	0.129 (7)	0.081 (5)	0.039 (3)	−0.076 (5)	−0.006 (4)	0.002 (3)

Geometric parameters (Å, º)

Cu1—N1	1.999 (4)	S42—C41	1.768 (5)
Cu1—S41	2.2599 (15)	S42—C43	1.773 (8)
Cu1—S21	2.4393 (14)	N1—C11	1.275 (6)
Cu1—S21^i	2.6702 (14)	N1—C13	1.463 (6)
Cu1—Cu4	2.7390 (10)	N2—C23	1.282 (6)
Cu1—Cu3	2.8120 (11)	N2—C21	1.458 (6)
Cu2—N2	2.021 (4)	N3—C31	1.280 (7)
Cu2—S31	2.2796 (14)	N3—C33	1.458 (7)
Cu2—S11	2.4463 (14)	N4—C41	1.275 (7)
Cu2—S11^ii	2.5880 (14)	N4—C42	1.451 (7)
Cu2—Cu4	2.7103 (10)	C12—C13	1.546 (7)
Cu2—Cu3	2.9041 (10)	C12—H12A	0.9700
Cu3—N4	2.002 (4)	C12—H12B	0.9700
Cu3—S21	2.2191 (13)	C13—H13A	0.9700
Cu3—S31	2.2912 (13)	C13—H13B	0.9700
Cu3—Cu4	2.9764 (10)	C21—C22	1.505 (8)
Cu4—N3	1.991 (4)	C21—H21A	0.9700
Cu4—S11	2.2250 (13)	C21—H21B	0.9700
Cu4—S41	2.3163 (14)	C22—H22A	0.9700
S11—C11	1.753 (5)	C22—H22B	0.9700
S11—Cu2^ii	2.5880 (14)	C32—C33	1.420 (10)
S12—C11	1.764 (5)	C32—H32A	0.9700
S12—C12	1.809 (5)	C32—H32B	0.9700
S21—C23	1.755 (4)	C33—H33A	0.9700
S21—Cu1^i	2.6702 (14)	C33—H33B	0.9700
S22—C23	1.762 (5)	C42—C43	1.487 (9)
S22—C22	1.802 (6)	C42—H42A	0.9700
S31—C31	1.746 (5)	C42—H42B	0.9700
S32—C31	1.763 (5)	C43—H43A	0.9700
S32—C32	1.799 (8)	C43—H43B	0.9700
S41—C41	1.741 (5)
N1—Cu1—S41	125.77 (12)	C31—S32—C32	88.9 (3)
N1—Cu1—S21	96.57 (12)	C41—S41—Cu1	107.98 (17)
S41—Cu1—S21	128.74 (5)	C41—S41—Cu4	98.81 (16)
N1—Cu1—S21^i	97.88 (12)	Cu1—S41—Cu4	73.52 (5)
S41—Cu1—S21^i	105.14 (5)	C41—S42—C43	90.0 (3)
S21—Cu1—S21^i	94.64 (4)	C11—N1—C13	114.2 (4)
N1—Cu1—Cu4	89.21 (11)	C11—N1—Cu1	126.1 (3)
S41—Cu1—Cu4	54.19 (4)	C13—N1—Cu1	117.6 (3)
S21—Cu1—Cu4	106.21 (4)	C23—N2—C21	114.1 (4)
S21^i—Cu1—Cu4	157.10 (4)	C23—N2—Cu2	127.7 (3)
N1—Cu1—Cu3	120.24 (12)	C21—N2—Cu2	117.9 (3)
S41—Cu1—Cu3	82.14 (4)	C31—N3—C33	112.4 (4)
S21—Cu1—Cu3	49.37 (3)	C31—N3—Cu4	119.3 (3)
S21^i—Cu1—Cu3	127.17 (4)	C33—N3—Cu4	126.6 (3)
Cu4—Cu1—Cu3	64.83 (3)	C41—N4—C42	113.2 (4)
N2—Cu2—S31	115.27 (12)	C41—N4—Cu3	121.5 (3)
N2—Cu2—S11	103.50 (12)	C42—N4—Cu3	124.8 (3)
S31—Cu2—S11	130.34 (5)	N1—C11—S11	125.2 (4)
N2—Cu2—S11^ii	102.35 (11)	N1—C11—S12	117.1 (4)
S31—Cu2—S11^ii	107.51 (5)	S11—C11—S12	117.6 (3)
S11—Cu2—S11^ii	92.35 (5)	C13—C12—S12	106.2 (3)
N2—Cu2—Cu4	122.25 (12)	C13—C12—H12A	110.5
S31—Cu2—Cu4	81.69 (4)	S12—C12—H12A	110.5
S11—Cu2—Cu4	50.81 (3)	C13—C12—H12B	110.5
S11^ii—Cu2—Cu4	125.58 (4)	S12—C12—H12B	110.5
N2—Cu2—Cu3	84.73 (11)	H12A—C12—H12B	108.7
S31—Cu2—Cu3	50.73 (3)	N1—C13—C12	110.9 (4)
S11—Cu2—Cu3	107.18 (4)	N1—C13—H13A	109.5
S11^ii—Cu2—Cu3	157.22 (4)	C12—C13—H13A	109.5
Cu4—Cu2—Cu3	63.92 (3)	N1—C13—H13B	109.5
N4—Cu3—S21	125.04 (12)	C12—C13—H13B	109.5
N4—Cu3—S31	105.99 (12)	H13A—C13—H13B	108.0
S21—Cu3—S31	128.84 (5)	N2—C21—C22	111.2 (4)
N4—Cu3—Cu1	89.37 (12)	N2—C21—H21A	109.4
S21—Cu3—Cu1	56.54 (4)	C22—C21—H21A	109.4
S31—Cu3—Cu1	127.56 (4)	N2—C21—H21B	109.4
N4—Cu3—Cu2	133.67 (12)	C22—C21—H21B	109.4
S21—Cu3—Cu2	87.35 (4)	H21A—C21—H21B	108.0
S31—Cu3—Cu2	50.38 (4)	C21—C22—S22	107.6 (4)
Cu1—Cu3—Cu2	82.64 (3)	C21—C22—H22A	110.2
N4—Cu3—Cu4	82.90 (12)	S22—C22—H22A	110.2
S21—Cu3—Cu4	104.91 (4)	C21—C22—H22B	110.2
S31—Cu3—Cu4	75.77 (4)	S22—C22—H22B	110.2
Cu1—Cu3—Cu4	56.40 (2)	H22A—C22—H22B	108.5
Cu2—Cu3—Cu4	54.87 (2)	N2—C23—S21	126.5 (4)
N3—Cu4—S11	124.54 (12)	N2—C23—S22	116.4 (3)
N3—Cu4—S41	105.20 (12)	S21—C23—S22	117.1 (3)
S11—Cu4—S41	129.78 (5)	N3—C31—S31	124.8 (4)
N3—Cu4—Cu2	90.31 (12)	N3—C31—S32	116.2 (4)
S11—Cu4—Cu2	58.44 (4)	S31—C31—S32	119.0 (3)
S41—Cu4—Cu2	134.30 (4)	C33—C32—S32	108.7 (5)
N3—Cu4—Cu1	138.32 (12)	C33—C32—H32A	109.9
S11—Cu4—Cu1	88.94 (4)	S32—C32—H32A	109.9
S41—Cu4—Cu1	52.30 (4)	C33—C32—H32B	109.9
Cu2—Cu4—Cu1	87.69 (3)	S32—C32—H32B	109.9
N3—Cu4—Cu3	84.11 (12)	H32A—C32—H32B	108.3
S11—Cu4—Cu3	111.28 (4)	C32—C33—N3	112.1 (5)
S41—Cu4—Cu3	77.66 (4)	C32—C33—H33A	109.2
Cu2—Cu4—Cu3	61.21 (2)	N3—C33—H33A	109.2
Cu1—Cu4—Cu3	58.77 (2)	C32—C33—H33B	109.2
C11—S11—Cu4	108.42 (15)	N3—C33—H33B	109.2
C11—S11—Cu2	98.03 (16)	H33A—C33—H33B	107.9
Cu4—S11—Cu2	70.75 (4)	N4—C41—S41	125.8 (4)
C11—S11—Cu2^ii	117.38 (16)	N4—C41—S42	116.3 (4)
Cu4—S11—Cu2^ii	131.58 (5)	S41—C41—S42	117.9 (3)
Cu2—S11—Cu2^ii	87.65 (5)	N4—C42—C43	111.1 (5)
C11—S12—C12	91.3 (2)	N4—C42—H42A	109.4
C23—S21—Cu3	107.26 (16)	C43—C42—H42A	109.4
C23—S21—Cu1	107.08 (16)	N4—C42—H42B	109.4
Cu3—S21—Cu1	74.09 (4)	C43—C42—H42B	109.4
C23—S21—Cu1^i	119.62 (16)	H42A—C42—H42B	108.0
Cu3—S21—Cu1^i	132.59 (5)	C42—C43—S42	108.0 (5)
Cu1—S21—Cu1^i	85.36 (4)	C42—C43—H43A	110.1
C23—S22—C22	90.7 (2)	S42—C43—H43A	110.1
C31—S31—Cu2	106.20 (17)	C42—C43—H43B	110.1
C31—S31—Cu3	98.64 (16)	S42—C43—H43B	110.1
Cu2—S31—Cu3	78.89 (5)	H43A—C43—H43B	108.4

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