Tetrakis(μ3-thio­urea)bis(μ2-thio­urea)octakis(thio­urea)hexa­copper(I) hexakis(perchlorate)

Athimoolam, S.; Kumar, J.; Ramakrishnan, V.; Rajaram, R.K.

doi:10.1107/S1600536805028588

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Tetrakis(μ₃-thiourea)bis(μ₂-thiourea)octakis(thiourea)hexacopper(I) hexakis(perchlorate)

S. Athimoolam, J. Kumar, V. Ramakrishnan and R. K. Rajaram

In the title compound, [Cu₆(CH₄N₂S)₁₄](ClO₄)₆, the interesting feature of the structure lies in the closely packed Cu–thiourea core, which is a truncated octahedron of two planes and four points at the edges. The octahedron is truncated parallel to the (101) plane. The Cu–thiourea core has pseudo-centrosymmetry about the centre of the octahedral void. The structure shows inter- and intramolecular N—H

S hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805028588/hg6222sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805028588/hg6222Isup2.hkl Contains datablock I

CCDC reference: 287590

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (l-O) = 0.011 Å
R factor = 0.038
wR factor = 0.110
Data-to-parameter ratio = 8.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT111_ALERT_2_B ADDSYM Detects (Pseudo) Centre of Symmetry .....         80 PerFit
PLAT111_ALERT_2_B ADDSYM Detects (Pseudo) Centre of Symmetry .....         80 PerFit
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu1    -   S9      ..      11.89 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu4    -   S12     ..      10.14 su
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for         C2
PLAT601_ALERT_2_B Structure Contains Solvent Accessible VOIDS of .     106.00 A   3  

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.65
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       7.97
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT213_ALERT_2_C Atom C5      has ADP max/min Ratio .............       3.30 prolat
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu2    -   S9      ..       7.07 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu2    -   S10     ..       7.91 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu3    -   S11     ..       7.63 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu3    -   S12     ..       6.77 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu3    -   S13     ..       5.78 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu4    -   S11     ..       8.72 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu5    -   S9      ..       7.03 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu5    -   S12     ..       8.21 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu6    -   S10     ..       7.79 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C5
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C7
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C11
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl1
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl2
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl3
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl4
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl5
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl6
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1B    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N3     -   H3B    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N5     -   H5A    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N6     -   H6B    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N8     -   H8B    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N9     -   H9A    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N10    -   H10A   ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N11    -   H11B   ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N15    -   H15B   ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N23    -   H23A   ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N27    -   H27A   ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N28    -   H28A   ...          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5B    ..  S13     ..       2.92 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6B    ..  S8      ..       3.00 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H23A   ..  O32     ..       2.61 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H23B   ..  S8      ..       2.89 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H27A   ..  S3      ..       2.97 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H28A   ..  S2      ..       2.98 Ang.
PLAT731_ALERT_1_C Bond    Calc  2.8072(16), Rep    2.807(4) ......       2.50 su-Rat
              CU1  -CU2     1.555   1.555
PLAT732_ALERT_1_C Angle   Calc   55.77(16), Rep    55.77(7) ......       2.29 su-Rat
              S10  -CU1  -CU2     1.555   1.555   1.555
PLAT732_ALERT_1_C Angle   Calc   56.13(16), Rep    56.13(7) ......       2.29 su-Rat
              S9   -CU2  -CU1     1.555   1.555   1.555
PLAT732_ALERT_1_C Angle   Calc   55.39(16), Rep    55.39(7) ......       2.29 su-Rat
              S12  -CU3  -CU4     1.555   1.555   1.555
PLAT732_ALERT_1_C Angle   Calc   55.01(16), Rep    55.00(7) ......       2.29 su-Rat
              S11  -CU4  -CU3     1.555   1.555   1.555
PLAT733_ALERT_1_C Torsion Calc -169.44(18), Rep  -169.44(7) ......       2.57 su-Rat
              S10 -CU1 -CU2 -S9     1.555   1.555   1.555   1.555
PLAT733_ALERT_1_C Torsion Calc  169.44(18), Rep   169.44(7) ......       2.57 su-Rat
              S9  -CU1 -CU2 -S10    1.555   1.555   1.555   1.555
PLAT733_ALERT_1_C Torsion Calc  169.17(18), Rep   169.17(7) ......       2.57 su-Rat
              S12 -CU3 -CU4 -S11    1.555   1.555   1.555   1.555
PLAT733_ALERT_1_C Torsion Calc -169.17(18), Rep  -169.17(7) ......       2.57 su-Rat
              S11 -CU3 -CU4 -S12    1.555   1.555   1.555   1.555
PLAT733_ALERT_1_C Torsion Calc   -8.74(17), Rep    -8.74(6) ......       2.83 su-Rat
              S10 -CU2 -S9  -CU1    1.555   1.555   1.555   1.555
PLAT733_ALERT_1_C Torsion Calc    9.13(17), Rep     9.13(6) ......       2.83 su-Rat
              S10 -CU1 -S9  -CU2    1.555   1.555   1.555   1.555
PLAT733_ALERT_1_C Torsion Calc   -8.72(17), Rep    -8.72(6) ......       2.83 su-Rat
              S9  -CU1 -S10 -CU2    1.555   1.555   1.555   1.555
PLAT733_ALERT_1_C Torsion Calc    9.19(17), Rep     9.19(6) ......       2.83 su-Rat
              S9  -CU2 -S10 -CU1    1.555   1.555   1.555   1.555
PLAT733_ALERT_1_C Torsion Calc    9.14(17), Rep     9.14(6) ......       2.83 su-Rat
              S12 -CU4 -S11 -CU3    1.555   1.555   1.555   1.555
PLAT733_ALERT_1_C Torsion Calc   -9.39(17), Rep    -9.39(6) ......       2.83 su-Rat
              S12 -CU3 -S11 -CU4    1.555   1.555   1.555   1.555
PLAT733_ALERT_1_C Torsion Calc    9.23(17), Rep     9.23(6) ......       2.83 su-Rat
              S11 -CU3 -S12 -CU4    1.555   1.555   1.555   1.555
PLAT733_ALERT_1_C Torsion Calc   -9.30(17), Rep    -9.31(6) ......       2.83 su-Rat
              S11 -CU4 -S12 -CU3    1.555   1.555   1.555   1.555

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C14 H56 Cl6 Cu6 N28 O24 S14
            Atom count from _chemical_formula_moiety:Cu2014
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.648
            Tmax scaled      0.647 Tmin scaled      0.568
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           24.98
           From the CIF: _reflns_number_total               6610
           Count of symmetry unique reflns         6419
           Completeness (_total/calc)            102.98%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       191
           Fraction of Friedel pairs measured     0.030
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   6 ALERT level B = Potentially serious problem
  60 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

  21 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  32 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
  14 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

In organic sulfur compounds, thiourea and its derivatives are of great importance. These compounds have been introduced in almost all branches of chemistry and they are commercialized as dyes, photographic films, elastometry plastics and textiles (Chynoweth, 1995). Thiourea complexes with gold(I) are of interest as medicines for the control of rheumatoid arthritis and in cancer chemotherapy (Parish & Cottrill, 1987). The crystal structures of bis(µ₂-thiourea)hexakis(thiourea)disilver(I) diperchlorate (Udupa & Krebs, 1973), bis[(µ₂-N,N-dimethylthiourea-S,S-bis(N,N'-dimethylthiourea-S)silver(I)] diperchlorate (Pakawatchai et al., 1996), bis(N,N'-dimethylthiourea-S)gold(I) perchlorate and bis(N,N'-diethylthiourea-S)gold(I) perchlorate (Staples et al., 1997), tetrathioureacopper(I) chloride (Lakshmi et al., 2003) and hexakis(thiourea)lead(II) perchlorate (Goldberg & Herbstein, 1972) have already been published. The formation of a complex of thiourea with copper perchlorate has already been reported as bis(µ₂-thiourea)tetrakis(thiourea)dicopper(I) diperchlorate in P2₁/c (Hanic & Durcahska, 1969).

In the present investigation, the title compound, (I), crystallized in the non-centrosymmetric space group Cc with six Cu^I cations, 14 thiourea molecules and six perchlorate anions in the asymmetric unit. The high coordination property of Cu with thiourea molecules leads to a truncated octahedron, a cage-like structure. Thiourea molecules coordinate two metal atoms through the S atom in such a manner that the distorted tetrahedral environment of every Cu atom includes four S atoms. This forms a closely packed Cu–thiourea cage, which has a void space inside (Filinchuk et al., 1990). During the structure analysis, it was observed that the unit cell contains large accessible voids in the crystal structure which tend to host disordered solvent water molecules. This affects the diffraction pattern, mostly at low scattering angles; this diffuse scattering effect was corrected with the SQUEEZE program (PLATON; Spek, 2003). Even though compound (I) crystallizes in a non-centrosymmetric space group, the truncated octahedron has a pseudo-inversion centre.

There are two metal–metal interactions in the structure of (I), with Cu···Cu distances of 2.807 (4) and 2.768 (3) Å, involving four Cu atoms (Cu1, Cu2, Cu3 and Cu4) to form a cross-sectional plane, with atoms S13 and S14 bisecting the octahedral core into two distorted pyramids (Table 1). Three types of Cu—S—Cu bond angles are observed in the Cu–thiourea cage of (I), namely normal (= 120°), short (<120°) and expanded (>120 °) (Table 1). The short Cu—S—Cu bonds are the consequence of the Cu···Cu interactions. The cage (truncated octahedron) is formed by four points (atoms) and two parallel planes (Fig 2). The four points are the centres of the atoms Cu5, Cu6, S13 and S14 and the two planes are formed by two sets of four atoms, namely Cu1—S9—Cu2—S10 and Cu3—S11—Cu4—S12. These two planes are parallel to the (101) plane of the unit cell, i.e. the octahedral shape is truncated parallel to the ac plane. The Cu···Cu interactions between these parallel planes through atoms S13 and S14, and the Cu···Cu interactions between the atoms in the planes (Cu1, Cu2, Cu3 and Cu4) with the Cu atoms in the edges (Cu5 and Cu6) through atoms S9, S10, S11 and S12, have expanded Cu—S—Cu angles. These expanded Cu—S—Cu angles lead to slightly elongated octahedra along the directions of the edges of the points. The faces of the octahedra can be obtained by leaving the four points (atoms) and treating six planes constituted by the sets of atoms Cu1/Cu2/S9/S10 (0.089 Å), Cu1/Cu4/S9/S12 (0.086 Å), Cu2/Cu3/S9/S12 (0.0176 Å), Cu3/Cu4/S11/S12 (0.0915 Å), Cu1/Cu4/S10/S11 (0.0157 Å) and Cu2/Cu3/S10/S11 (0.0084 Å) (the values in parentheses are the r.m.s. deviations of the fitted atoms in the mean plane). The angles between these planes of the truncated octahedron vary from 54.0 (2) to 89.8 (2)°.

All the thiourea groups in (I) are planar. Of the 14 thiourea molecules, eight are outside the cage (S1–S8) and not involved in bridging between Cu atoms. In the other six thiourea molecules, two (S13 and S14) each bridge two Cu atoms as µ₂-bridging ligands and the other four participate in µ₃-bridging. The tetrahedral geometry of the CuS₄ group is disturbed because of the different coordination nature of the thiourea molecules in relation to the Cu atoms.

All the perchlorate groups show nearly tetrahedral symmetry and play a vital role in hydrogen bonding, which stabilizes the crystal structure. The average Cl—O bond distances and O—Cl—O bond angles are 1.407 Å and 109.45°, respectively (Table 1).

The S atoms which are just outside the Cu—thiourea core participate in strong and moderate hydrogen bonding. The N9—H9B···S7ⁱ intermolecular bond seems to be a strong bond [3.276 Å and 174.66°]. Interestingly, there is only one N—H···N hydrogen bond (N2—H2A···N14) found in the three-centred hydrogen-bonding network. The N—H···O hydrogen bonds between the thiourea molecules and the perchlorate groups seem to be moderate hydrogen bonds. The excess of acceptor atoms in the structure leads to a large number of three-centred hydrogen bonds (Table 2).

Experimental top

Cu(ClO₄)₂·6H₂O (2.0 g, 5.40 mmol) and thiourea (2.25 g, 29.6 mmol) were mixed in water (50 ml) and heated slightly over a water bath to give complete dissolution. Slow evaporation of the solvent yielded a white crystalline powder which was recrystallized in triply distilled water to yield white single crystals of the title complex. Caution: Although no problems were encountered in this work, all perchlorate compounds are potentially explosive and should be prepared in small amounts and handled with care.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXTL/PC (Bruker, 2000); program(s) used to refine structure: SHELXTL/PC; molecular graphics: SHELXTL/PC and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme and 50% probability displacement ellipsoids.
	Fig. 2. The Cu–thiourea cage – a truncated octahedron.
	Fig. 3. A packing diagram of the molecule, viewed down the b axis.

Tetrakis(µ₃-thiourea)bis(µ₂-thiourea)octakis(thiourea)hexacopper(I) hexaperchlorate top

Crystal data top

[Cu₆(CH₄N₂S)₁₄](ClO₄)₆	F(000) = 4112
M_r = 2043.65	D_x = 1.859 Mg m⁻³ D_m = 1.845 Mg m⁻³ D_m measured by flotation using a mixture of CCl₄ and CHBr₃
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 25 reflections
a = 17.229 (2) Å	θ = 11.2–13.6°
b = 15.363 (3) Å	µ = 2.42 mm⁻¹
c = 27.639 (5) Å	T = 293 K
β = 93.30 (15)°	Block, white
V = 7304 (2) Å³	0.24 × 0.2 × 0.18 mm
Z = 4

Data collection top

Nonius MACH3 diffractometer	5203 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.046
Graphite monochromator	θ_max = 25.0°, θ_min = 2.3°
ω/2θ scans	h = 0→20
Absorption correction: ψ scan (North et al., 1968)	k = −1→18
T_min = 0.568, T_max = 0.647	l = −32→32
7120 measured reflections	3 standard reflections every 60 min
6610 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0685P)² + 13.3767P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
6610 reflections	Δρ_max = 1.22 e Å⁻³
829 parameters	Δρ_min = −0.86 e Å⁻³
4 restraints	Absolute structure: Flack (1983), with how many Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.015 (17)

Crystal data top

[Cu₆(CH₄N₂S)₁₄](ClO₄)₆	V = 7304 (2) Å³
M_r = 2043.65	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 17.229 (2) Å	µ = 2.42 mm⁻¹
b = 15.363 (3) Å	T = 293 K
c = 27.639 (5) Å	0.24 × 0.2 × 0.18 mm
β = 93.30 (15)°

Data collection top

Nonius MACH3 diffractometer	5203 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.046
T_min = 0.568, T_max = 0.647	3 standard reflections every 60 min
7120 measured reflections	intensity decay: none
6610 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0685P)² + 13.3767P] where P = (F_o² + 2F_c²)/3
S = 1.03	Δρ_max = 1.22 e Å⁻³
6610 reflections	Δρ_min = −0.86 e Å⁻³
829 parameters	Absolute structure: Flack (1983), with how many Friedel pairs
4 restraints	Absolute structure parameter: 0.015 (17)

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.39499 (6)	0.35940 (7)	0.79039 (4)	0.0360 (3)
Cu2	0.52925 (6)	0.35676 (7)	0.73748 (4)	0.0357 (3)
Cu3	0.52624 (6)	0.61945 (7)	0.73507 (4)	0.0360 (3)
Cu4	0.39009 (7)	0.62087 (7)	0.78359 (4)	0.0389 (3)
Cu5	0.37508 (8)	0.48447 (8)	0.64555 (5)	0.0428 (3)
Cu6	0.55072 (9)	0.49271 (7)	0.87489 (5)	0.0417 (3)
S1	0.32822 (16)	0.23351 (16)	0.80336 (9)	0.0403 (6)
S2	0.59680 (16)	0.23248 (16)	0.72392 (9)	0.0404 (6)
S3	0.59435 (16)	0.74028 (16)	0.71645 (9)	0.0419 (6)
S4	0.32208 (16)	0.74303 (16)	0.80090 (9)	0.0429 (6)
S5	0.4611 (2)	0.4820 (2)	0.58274 (12)	0.0607 (8)
S6	0.6811 (2)	0.49340 (16)	0.89607 (11)	0.0471 (8)
S7	0.4520 (2)	0.50453 (18)	0.92747 (11)	0.0584 (9)
S8	0.24230 (18)	0.48744 (17)	0.62833 (11)	0.0434 (7)
S9	0.40330 (14)	0.36978 (14)	0.70220 (7)	0.0294 (5)
S10	0.52121 (14)	0.36953 (14)	0.82502 (8)	0.0306 (5)
S11	0.51676 (14)	0.60994 (15)	0.82114 (8)	0.0309 (5)
S12	0.40063 (14)	0.60656 (14)	0.69741 (8)	0.0314 (5)
S13	0.58555 (16)	0.48758 (13)	0.71764 (9)	0.0309 (6)
S14	0.33294 (15)	0.48930 (13)	0.80586 (9)	0.0298 (5)
C1	0.3105 (7)	0.2397 (7)	0.8645 (4)	0.050 (3)
C2	0.6265 (6)	0.2413 (7)	0.6663 (3)	0.040 (2)
C3	0.5994 (6)	0.7381 (7)	0.6557 (3)	0.038 (2)
C4	0.3179 (6)	0.7419 (6)	0.8636 (4)	0.045 (3)
C5	0.4642 (8)	0.3760 (9)	0.5644 (3)	0.066 (4)
C6	0.6997 (7)	0.5152 (6)	0.9560 (4)	0.047 (3)
C7	0.4475 (6)	0.4109 (7)	0.9592 (3)	0.046 (2)
C8	0.2179 (6)	0.4741 (6)	0.5674 (4)	0.046 (3)
C9	0.3652 (6)	0.2720 (6)	0.6805 (3)	0.036 (2)
C10	0.5574 (5)	0.2723 (6)	0.8506 (3)	0.034 (2)
C11	0.5509 (6)	0.7074 (7)	0.8472 (4)	0.043 (2)
C12	0.3762 (6)	0.7018 (6)	0.6657 (4)	0.039 (2)
C13	0.6737 (7)	0.4901 (6)	0.7482 (4)	0.035 (2)
C14	0.2425 (6)	0.4851 (6)	0.7739 (4)	0.034 (2)
N1	0.3162 (8)	0.1707 (8)	0.8919 (4)	0.081 (4)
H1A	0.3096	0.1748	0.9224	0.097*
H1B	0.3265	0.1210	0.8795	0.097*
N2	0.2948 (7)	0.3138 (6)	0.8849 (4)	0.072 (3)
H2A	0.2885	0.3160	0.9155	0.087*
H2B	0.2907	0.3604	0.8677	0.087*
N3	0.6342 (9)	0.1702 (7)	0.6418 (4)	0.103 (5)
H3A	0.6530	0.1720	0.6137	0.124*
H3B	0.6207	0.1212	0.6538	0.124*
N4	0.6470 (8)	0.3130 (6)	0.6480 (4)	0.079 (4)
H4A	0.6656	0.3139	0.6198	0.095*
H4B	0.6422	0.3607	0.6638	0.095*
N5	0.5925 (8)	0.6674 (7)	0.6276 (4)	0.082 (4)
H5A	0.5953	0.6720	0.5967	0.099*
H5B	0.5852	0.6172	0.6403	0.099*
N6	0.6106 (7)	0.8121 (6)	0.6321 (4)	0.066 (3)
H6A	0.6128	0.8119	0.6011	0.079*
H6B	0.6155	0.8602	0.6479	0.079*
N7	0.3156 (6)	0.6701 (5)	0.8888 (3)	0.059 (3)
H7A	0.3122	0.6723	0.9197	0.071*
H7B	0.3175	0.6205	0.8744	0.071*
N8	0.3148 (6)	0.8182 (6)	0.8875 (4)	0.055 (2)
H8A	0.3115	0.8187	0.9184	0.066*
H8B	0.3162	0.8665	0.8718	0.066*
N9	0.4613 (9)	0.3538 (7)	0.5162 (4)	0.097 (4)
H9A	0.4623	0.2999	0.5079	0.117*
H9B	0.4585	0.3937	0.4944	0.117*
N10	0.4683 (9)	0.3094 (8)	0.5924 (5)	0.117 (5)
H10A	0.4690	0.2579	0.5803	0.140*
H10B	0.4704	0.3163	0.6234	0.140*
N11	0.7710 (6)	0.5199 (6)	0.9738 (4)	0.058 (3)
H11A	0.7804	0.5335	1.0037	0.069*
H11B	0.8087	0.5094	0.9556	0.069*
N12	0.6412 (7)	0.5320 (7)	0.9853 (3)	0.069 (3)
H12A	0.6515	0.5455	1.0151	0.083*
H12B	0.5937	0.5291	0.9740	0.083*
N13	0.5075 (6)	0.3591 (6)	0.9661 (4)	0.078 (3)
H13A	0.5034	0.3119	0.9826	0.094*
H13B	0.5511	0.3722	0.9543	0.094*
N14	0.3828 (6)	0.3880 (7)	0.9779 (4)	0.073 (3)
H14A	0.3806	0.3404	0.9942	0.087*
H14B	0.3423	0.4205	0.9741	0.087*
N15	0.1442 (6)	0.4725 (6)	0.5519 (3)	0.059 (3)
H15A	0.1318	0.4653	0.5215	0.071*
H15B	0.1084	0.4786	0.5721	0.071*
N16	0.2725 (6)	0.4645 (6)	0.5357 (3)	0.055 (2)
H16A	0.2596	0.4573	0.5055	0.066*
H16B	0.3208	0.4654	0.5455	0.066*
N17	0.3997 (6)	0.1978 (6)	0.6907 (3)	0.049 (2)
H17A	0.3799	0.1500	0.6795	0.059*
H17B	0.4422	0.1968	0.7086	0.059*
N18	0.2994 (5)	0.2737 (6)	0.6527 (3)	0.051 (2)
H18A	0.2795	0.2259	0.6415	0.061*
H18B	0.2768	0.3225	0.6461	0.061*
N19	0.6184 (6)	0.2740 (6)	0.8781 (3)	0.056 (2)
H19A	0.6386	0.2263	0.8891	0.067*
H19B	0.6399	0.3230	0.8858	0.067*
N20	0.5232 (6)	0.1979 (5)	0.8382 (4)	0.054 (3)
H20A	0.5426	0.1495	0.8488	0.065*
H20B	0.4816	0.1979	0.8194	0.065*
N21	0.6091 (7)	0.7048 (7)	0.8768 (4)	0.093 (4)
H21A	0.6297	0.7524	0.8878	0.112*
H21B	0.6283	0.6555	0.8861	0.112*
N22	0.5213 (6)	0.7819 (5)	0.8329 (4)	0.057 (3)
H22A	0.5416	0.8297	0.8437	0.069*
H22B	0.4815	0.7831	0.8126	0.069*
N23	0.3380 (6)	0.6971 (6)	0.6243 (4)	0.074 (3)
H23A	0.3245	0.7439	0.6089	0.089*
H23B	0.3259	0.6471	0.6120	0.089*
N24	0.3948 (6)	0.7779 (6)	0.6847 (3)	0.052 (3)
H24A	0.3815	0.8249	0.6695	0.063*
H24B	0.4203	0.7807	0.7123	0.063*
N25	0.7106 (5)	0.4168 (6)	0.7622 (3)	0.051 (2)
H25A	0.7565	0.4193	0.7761	0.061*
H25B	0.6883	0.3672	0.7573	0.061*
N26	0.7120 (6)	0.5648 (5)	0.7570 (4)	0.052 (2)
H26A	0.7579	0.5639	0.7710	0.063*
H26B	0.6908	0.6135	0.7487	0.063*
N27	0.2128 (5)	0.4106 (6)	0.7608 (3)	0.051 (2)
H27A	0.1692	0.4087	0.7440	0.061*
H27B	0.2367	0.3632	0.7688	0.061*
N28	0.2070 (5)	0.5581 (6)	0.7620 (4)	0.054 (2)
H28A	0.1633	0.5570	0.7453	0.065*
H28B	0.2273	0.6071	0.7710	0.065*
Cl1	0.92944 (17)	0.48784 (15)	0.78929 (12)	0.0606 (7)
O11	0.9867 (7)	0.4901 (9)	0.8268 (5)	0.122 (5)
O12	0.8552 (4)	0.4874 (5)	0.8120 (4)	0.073 (2)
O13	0.9423 (7)	0.4119 (5)	0.7615 (4)	0.100 (4)
O14	0.9389 (9)	0.5618 (6)	0.7622 (4)	0.134 (6)
Cl2	0.7728 (2)	0.50528 (16)	0.61840 (11)	0.0494 (7)
O21	0.7744 (7)	0.5811 (7)	0.6482 (4)	0.093 (3)
O22	0.7970 (7)	0.4356 (7)	0.6472 (4)	0.098 (3)
O23	0.8191 (8)	0.5145 (7)	0.5781 (4)	0.099 (4)
O24	0.6947 (7)	0.4921 (6)	0.5999 (4)	0.080 (3)
Cl3	0.45151 (17)	0.84322 (18)	0.53001 (12)	0.0659 (7)
O31	0.5214 (6)	0.7954 (8)	0.5297 (4)	0.115 (4)
O32	0.4295 (8)	0.8502 (8)	0.5789 (4)	0.127 (5)
O33	0.3915 (6)	0.8029 (8)	0.5030 (6)	0.143 (5)
O34	0.4612 (8)	0.9315 (6)	0.5129 (4)	0.112 (4)
Cl4	0.69561 (16)	0.23546 (15)	0.51717 (9)	0.0461 (6)
O41	0.7119 (7)	0.3094 (5)	0.5469 (3)	0.085 (3)
O42	0.6195 (7)	0.2111 (11)	0.5244 (6)	0.161 (6)
O43	0.7113 (6)	0.2561 (7)	0.4688 (3)	0.090 (3)
O44	0.7436 (7)	0.1674 (6)	0.5342 (3)	0.099 (3)
Cl5	0.72539 (16)	0.73552 (16)	0.50491 (10)	0.0485 (6)
O51	0.7994 (6)	0.7025 (11)	0.4948 (4)	0.138 (5)
O52	0.7252 (9)	0.7596 (7)	0.5529 (3)	0.121 (5)
O53	0.6732 (7)	0.6702 (7)	0.4938 (6)	0.133 (5)
O54	0.7065 (6)	0.8078 (6)	0.4742 (3)	0.084 (3)
Cl6	0.14953 (18)	0.49183 (16)	0.90827 (10)	0.0452 (7)
O61	0.2266 (5)	0.4905 (5)	0.9286 (4)	0.062 (2)
O62	0.0980 (8)	0.5030 (9)	0.9435 (5)	0.124 (6)
O63	0.1428 (6)	0.5656 (6)	0.8757 (4)	0.087 (3)
O64	0.1345 (6)	0.4134 (6)	0.8824 (4)	0.095 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0389 (7)	0.0262 (6)	0.0430 (7)	0.0000 (5)	0.0042 (5)	0.0039 (5)
Cu2	0.0415 (7)	0.0255 (6)	0.0405 (6)	0.0006 (5)	0.0037 (5)	−0.0007 (5)
Cu3	0.0446 (7)	0.0241 (6)	0.0394 (6)	−0.0014 (5)	0.0019 (5)	0.0053 (5)
Cu4	0.0454 (7)	0.0269 (6)	0.0447 (7)	−0.0002 (5)	0.0053 (6)	−0.0021 (5)
Cu5	0.0548 (9)	0.0341 (6)	0.0379 (7)	−0.0027 (6)	−0.0114 (6)	0.0017 (5)
Cu6	0.0560 (9)	0.0320 (6)	0.0355 (7)	−0.0006 (5)	−0.0108 (6)	0.0036 (5)
S1	0.0514 (15)	0.0262 (12)	0.0437 (13)	−0.0085 (11)	0.0050 (12)	−0.0015 (10)
S2	0.0542 (16)	0.0254 (12)	0.0423 (14)	0.0098 (11)	0.0084 (12)	0.0028 (10)
S3	0.0606 (17)	0.0268 (12)	0.0381 (13)	−0.0107 (12)	0.0012 (12)	0.0028 (10)
S4	0.0567 (16)	0.0251 (12)	0.0466 (14)	0.0107 (11)	−0.0002 (12)	0.0004 (10)
S5	0.066 (2)	0.0590 (17)	0.0572 (18)	−0.0151 (15)	0.0060 (15)	0.0162 (14)
S6	0.0551 (19)	0.0394 (15)	0.0443 (16)	0.0028 (11)	−0.0171 (15)	−0.0042 (10)
S7	0.077 (2)	0.0574 (17)	0.0418 (15)	0.0221 (14)	0.0106 (15)	0.0039 (12)
S8	0.0480 (17)	0.0403 (14)	0.0403 (15)	0.0009 (11)	−0.0125 (13)	−0.0030 (11)
S9	0.0402 (14)	0.0236 (11)	0.0233 (11)	0.0004 (10)	−0.0062 (10)	−0.0004 (8)
S10	0.0418 (14)	0.0219 (11)	0.0272 (11)	0.0021 (10)	−0.0054 (10)	0.0000 (8)
S11	0.0437 (14)	0.0219 (11)	0.0262 (11)	0.0007 (10)	−0.0059 (10)	0.0013 (8)
S12	0.0461 (14)	0.0202 (10)	0.0267 (11)	−0.0006 (10)	−0.0095 (10)	0.0021 (8)
S13	0.0394 (15)	0.0194 (11)	0.0333 (13)	0.0013 (10)	−0.0037 (11)	−0.0002 (9)
S14	0.0334 (14)	0.0216 (11)	0.0340 (12)	0.0021 (9)	−0.0016 (11)	0.0011 (9)
C1	0.054 (6)	0.030 (5)	0.068 (7)	−0.012 (5)	0.023 (5)	0.011 (5)
C2	0.055 (6)	0.041 (6)	0.026 (5)	−0.005 (5)	0.009 (4)	−0.012 (4)
C3	0.032 (5)	0.046 (6)	0.037 (5)	−0.001 (4)	0.000 (4)	0.009 (4)
C4	0.040 (5)	0.030 (5)	0.065 (7)	0.010 (4)	0.008 (5)	−0.003 (5)
C5	0.098 (9)	0.085 (9)	0.018 (4)	0.043 (7)	0.010 (5)	0.019 (5)
C6	0.067 (7)	0.022 (4)	0.050 (6)	0.004 (5)	−0.012 (6)	−0.001 (4)
C7	0.048 (6)	0.047 (6)	0.042 (5)	−0.005 (5)	0.001 (4)	0.010 (4)
C8	0.068 (7)	0.012 (4)	0.053 (6)	−0.007 (4)	−0.021 (6)	0.001 (4)
C9	0.058 (6)	0.024 (5)	0.027 (4)	−0.009 (4)	0.016 (4)	−0.003 (4)
C10	0.030 (5)	0.032 (5)	0.041 (5)	0.004 (4)	−0.004 (4)	0.005 (4)
C11	0.046 (6)	0.037 (5)	0.045 (6)	−0.001 (5)	−0.008 (5)	0.003 (4)
C12	0.042 (5)	0.027 (5)	0.048 (6)	−0.004 (4)	−0.004 (4)	0.014 (4)
C13	0.035 (6)	0.033 (5)	0.038 (5)	0.005 (4)	0.008 (5)	−0.002 (4)
C14	0.035 (6)	0.037 (5)	0.028 (5)	−0.001 (4)	−0.003 (4)	0.000 (4)
N1	0.112 (9)	0.074 (7)	0.055 (6)	0.007 (6)	−0.005 (6)	0.035 (5)
N2	0.128 (10)	0.042 (5)	0.051 (5)	−0.006 (6)	0.046 (6)	−0.002 (4)
N3	0.194 (16)	0.042 (6)	0.080 (8)	0.000 (8)	0.061 (9)	−0.020 (5)
N4	0.134 (11)	0.046 (6)	0.063 (7)	−0.017 (6)	0.050 (7)	−0.014 (5)
N5	0.138 (11)	0.067 (7)	0.042 (6)	−0.025 (7)	0.013 (6)	−0.002 (5)
N6	0.098 (8)	0.042 (5)	0.058 (6)	−0.027 (5)	0.005 (6)	0.019 (5)
N7	0.105 (8)	0.030 (5)	0.044 (5)	0.005 (5)	0.027 (5)	0.005 (4)
N8	0.068 (6)	0.041 (5)	0.056 (5)	−0.004 (5)	0.006 (5)	−0.005 (4)
N9	0.158 (11)	0.073 (7)	0.061 (7)	0.013 (8)	0.008 (7)	0.003 (6)
N10	0.195 (15)	0.065 (7)	0.098 (10)	0.007 (9)	0.072 (10)	−0.002 (7)
N11	0.063 (6)	0.060 (6)	0.047 (5)	0.002 (5)	−0.032 (5)	0.002 (4)
N12	0.095 (8)	0.067 (6)	0.044 (5)	−0.005 (6)	−0.012 (5)	−0.018 (5)
N13	0.062 (6)	0.063 (6)	0.112 (9)	0.005 (5)	0.020 (6)	0.050 (6)
N14	0.058 (6)	0.071 (6)	0.090 (7)	−0.005 (5)	0.010 (5)	−0.008 (6)
N15	0.057 (6)	0.065 (6)	0.050 (5)	−0.017 (5)	−0.039 (4)	0.007 (5)
N16	0.062 (6)	0.076 (6)	0.025 (4)	−0.010 (5)	−0.022 (4)	0.005 (4)
N17	0.066 (6)	0.033 (5)	0.046 (5)	−0.002 (4)	−0.023 (4)	−0.009 (4)
N18	0.038 (5)	0.038 (5)	0.075 (6)	−0.004 (4)	−0.020 (4)	−0.014 (4)
N19	0.070 (6)	0.040 (5)	0.055 (6)	0.012 (5)	−0.020 (5)	0.008 (4)
N20	0.058 (6)	0.021 (4)	0.082 (7)	0.004 (4)	−0.006 (5)	0.013 (4)
N21	0.121 (10)	0.041 (5)	0.107 (9)	0.000 (6)	−0.077 (8)	−0.021 (6)
N22	0.079 (7)	0.015 (4)	0.077 (7)	−0.002 (4)	−0.008 (5)	0.000 (4)
N23	0.115 (9)	0.025 (4)	0.076 (7)	−0.012 (5)	−0.052 (6)	0.014 (4)
N24	0.083 (7)	0.032 (5)	0.040 (5)	0.001 (5)	−0.019 (5)	0.007 (4)
N25	0.053 (5)	0.037 (5)	0.060 (6)	0.001 (4)	−0.019 (4)	0.009 (4)
N26	0.049 (5)	0.024 (4)	0.081 (7)	−0.007 (4)	−0.022 (5)	0.001 (4)
N27	0.048 (5)	0.038 (5)	0.065 (6)	−0.003 (4)	−0.011 (4)	0.004 (4)
N28	0.041 (5)	0.044 (5)	0.077 (7)	0.007 (4)	−0.009 (5)	0.004 (5)
Cl1	0.0636 (17)	0.0324 (12)	0.0834 (19)	0.0000 (11)	−0.0161 (14)	0.0029 (12)
O11	0.081 (7)	0.181 (13)	0.101 (8)	0.003 (7)	−0.036 (7)	−0.020 (7)
O12	0.033 (4)	0.083 (6)	0.102 (7)	−0.002 (4)	0.002 (4)	−0.001 (5)
O13	0.173 (12)	0.048 (4)	0.080 (6)	−0.016 (6)	0.013 (7)	−0.014 (5)
O14	0.254 (18)	0.054 (5)	0.099 (7)	0.044 (8)	0.060 (9)	0.033 (6)
Cl2	0.061 (2)	0.0374 (13)	0.0506 (16)	−0.0038 (11)	0.0120 (15)	−0.0021 (10)
O21	0.136 (10)	0.068 (6)	0.074 (6)	−0.017 (6)	−0.005 (6)	−0.020 (5)
O22	0.126 (9)	0.078 (7)	0.088 (7)	0.012 (6)	0.001 (6)	0.029 (6)
O23	0.092 (8)	0.135 (10)	0.074 (7)	−0.011 (7)	0.030 (7)	0.020 (6)
O24	0.085 (8)	0.084 (7)	0.069 (6)	−0.011 (5)	−0.015 (6)	−0.011 (5)
Cl3	0.0578 (16)	0.0562 (16)	0.084 (2)	0.0054 (13)	0.0028 (15)	−0.0030 (14)
O31	0.079 (6)	0.141 (9)	0.122 (9)	0.048 (6)	−0.033 (6)	−0.071 (7)
O32	0.195 (13)	0.117 (9)	0.076 (7)	0.006 (8)	0.068 (8)	0.027 (6)
O33	0.072 (7)	0.114 (9)	0.236 (16)	−0.003 (6)	−0.056 (9)	−0.031 (10)
O34	0.177 (10)	0.074 (6)	0.083 (6)	−0.044 (7)	−0.002 (6)	0.012 (5)
Cl4	0.0538 (17)	0.0455 (14)	0.0393 (14)	0.0087 (11)	0.0058 (12)	−0.0034 (10)
O41	0.157 (9)	0.056 (5)	0.045 (5)	−0.005 (5)	0.036 (5)	−0.012 (4)
O42	0.067 (7)	0.192 (15)	0.229 (17)	−0.039 (8)	0.052 (9)	−0.056 (13)
O43	0.119 (8)	0.128 (8)	0.024 (4)	0.005 (7)	0.001 (4)	0.007 (4)
O44	0.157 (10)	0.060 (5)	0.076 (6)	0.026 (6)	−0.032 (6)	0.004 (4)
Cl5	0.0533 (16)	0.0490 (15)	0.0431 (14)	−0.0104 (12)	0.0019 (12)	−0.0071 (11)
O51	0.074 (7)	0.246 (16)	0.096 (8)	0.056 (9)	0.034 (6)	0.045 (9)
O52	0.246 (16)	0.086 (7)	0.031 (5)	0.014 (8)	0.004 (7)	0.004 (4)
O53	0.096 (8)	0.073 (7)	0.222 (15)	−0.024 (6)	−0.056 (9)	0.003 (8)
O54	0.137 (8)	0.074 (5)	0.037 (4)	−0.021 (5)	−0.023 (5)	0.011 (4)
Cl6	0.0512 (17)	0.0467 (14)	0.0367 (13)	0.0042 (11)	−0.0067 (13)	−0.0054 (10)
O61	0.050 (5)	0.064 (6)	0.068 (6)	0.015 (4)	−0.018 (4)	−0.008 (4)
O62	0.069 (7)	0.229 (19)	0.075 (8)	−0.009 (7)	0.014 (7)	−0.047 (8)
O63	0.087 (6)	0.066 (6)	0.104 (7)	0.005 (5)	−0.032 (6)	0.044 (5)
O64	0.096 (7)	0.046 (5)	0.137 (9)	0.009 (5)	−0.057 (6)	−0.033 (5)

Geometric parameters (Å, º) top

Cu1—S1	2.289 (3)	N4—H4A	0.8600
Cu1—S14	2.315 (3)	N4—H4B	0.8600
Cu1—S10	2.330 (4)	N5—H5A	0.8600
Cu1—S9	2.455 (2)	N5—H5B	0.8600
Cu1—Cu2	2.807 (4)	N6—H6A	0.8600
Cu2—S2	2.278 (3)	N6—H6B	0.8600
Cu2—S13	2.311 (3)	N7—H7A	0.8600
Cu2—S9	2.336 (4)	N7—H7B	0.8600
Cu2—S10	2.439 (3)	N8—H8A	0.8600
Cu3—S3	2.271 (3)	N8—H8B	0.8600
Cu3—S13	2.332 (3)	N9—H9A	0.8600
Cu3—S12	2.355 (4)	N9—H9B	0.8600
Cu3—S11	2.398 (3)	N10—H10A	0.8600
Cu3—Cu4	2.768 (3)	N10—H10B	0.8600
Cu4—S4	2.278 (3)	N11—H11A	0.8600
Cu4—S14	2.346 (3)	N11—H11B	0.8600
Cu4—S11	2.368 (4)	N12—H12A	0.8600
Cu4—S12	2.409 (3)	N12—H12B	0.8600
Cu5—S8	2.310 (4)	N13—H13A	0.8600
Cu5—S5	2.347 (5)	N13—H13B	0.8600
Cu5—S12	2.386 (3)	N14—H14A	0.8600
Cu5—S9	2.388 (3)	N14—H14B	0.8600
Cu6—S6	2.289 (4)	N15—H15A	0.8600
Cu6—S7	2.307 (5)	N15—H15B	0.8600
Cu6—S10	2.379 (3)	N16—H16A	0.8600
Cu6—S11	2.386 (3)	N16—H16B	0.8600
S1—C1	1.737 (12)	N17—H17A	0.8600
S2—C2	1.707 (9)	N17—H17B	0.8600
S3—C3	1.688 (10)	N18—H18A	0.8600
S4—C4	1.739 (11)	N18—H18B	0.8600
S5—C5	1.706 (13)	N19—H19A	0.8600
S6—C6	1.703 (11)	N19—H19B	0.8600
S7—C7	1.689 (10)	N20—H20A	0.8600
S8—C8	1.724 (10)	N20—H20B	0.8600
S9—C9	1.732 (9)	N21—H21A	0.8600
S10—C10	1.752 (9)	N21—H21B	0.8600
S11—C11	1.748 (11)	N22—H22A	0.8600
S12—C12	1.745 (9)	N22—H22B	0.8600
S13—C13	1.696 (12)	N23—H23A	0.8600
S14—C14	1.747 (11)	N23—H23B	0.8600
C1—N1	1.303 (14)	N24—H24A	0.8600
C1—N2	1.306 (14)	N24—H24B	0.8600
C2—N4	1.271 (13)	N25—H25A	0.8600
C2—N3	1.295 (13)	N25—H25B	0.8600
C3—N6	1.329 (13)	N26—H26A	0.8600
C3—N5	1.338 (14)	N26—H26B	0.8600
C4—N7	1.307 (13)	N27—H27A	0.8600
C4—N8	1.348 (13)	N27—H27B	0.8600
C5—N10	1.283 (15)	N28—H28A	0.8600
C5—N9	1.373 (15)	N28—H28B	0.8600
C6—N11	1.297 (15)	Cl1—O14	1.375 (9)
C6—N12	1.353 (15)	Cl1—O11	1.389 (11)
C7—N14	1.305 (13)	Cl1—O13	1.422 (9)
C7—N13	1.310 (13)	Cl1—O12	1.457 (9)
C8—N15	1.317 (13)	Cl2—O22	1.384 (10)
C8—N16	1.331 (14)	Cl2—O23	1.415 (12)
C9—N17	1.310 (13)	Cl2—O24	1.425 (12)
C9—N18	1.332 (13)	Cl2—O21	1.426 (10)
C10—N19	1.262 (13)	Cl3—O33	1.386 (11)
C10—N20	1.321 (13)	Cl3—O31	1.411 (9)
C11—N21	1.258 (14)	Cl3—O32	1.428 (10)
C11—N22	1.305 (13)	Cl3—O34	1.450 (9)
C12—N23	1.289 (13)	Cl4—O42	1.390 (11)
C12—N24	1.313 (13)	Cl4—O44	1.397 (9)
C13—N25	1.339 (13)	Cl4—O43	1.415 (9)
C13—N26	1.339 (13)	Cl4—O41	1.421 (8)
C14—N27	1.297 (13)	Cl5—O53	1.370 (10)
C14—N28	1.310 (13)	Cl5—O52	1.376 (9)
N1—H1A	0.8600	Cl5—O51	1.416 (10)
N1—H1B	0.8600	Cl5—O54	1.423 (9)
N2—H2A	0.8600	Cl6—O62	1.365 (14)
N2—H2B	0.8600	Cl6—O61	1.412 (10)
N3—H3A	0.8600	Cl6—O64	1.417 (9)
N3—H3B	0.8600	Cl6—O63	1.448 (9)

S1—Cu1—S14	117.24 (12)	N25—C13—N26	116.6 (11)
S1—Cu1—S10	117.24 (10)	N25—C13—S13	121.4 (8)
S14—Cu1—S10	107.25 (9)	N26—C13—S13	121.9 (8)
S1—Cu1—S9	105.60 (12)	N27—C14—N28	120.9 (10)
S14—Cu1—S9	100.44 (11)	N27—C14—S14	120.0 (8)
S10—Cu1—S9	107.28 (16)	N28—C14—S14	119.1 (8)
S1—Cu1—Cu2	120.39 (9)	C1—N1—H1A	120.0
S14—Cu1—Cu2	120.78 (9)	C1—N1—H1B	120.0
S10—Cu1—Cu2	55.77 (7)	H1A—N1—H1B	120.0
S9—Cu1—Cu2	52.18 (12)	C1—N2—H2A	120.0
S2—Cu2—S13	117.66 (12)	C1—N2—H2B	120.0
S2—Cu2—S9	118.31 (10)	H2A—N2—H2B	120.0
S13—Cu2—S9	102.65 (9)	C2—N3—H3A	120.0
S2—Cu2—S10	106.82 (12)	C2—N3—H3B	120.0
S13—Cu2—S10	102.36 (11)	H3A—N3—H3B	120.0
S9—Cu2—S10	107.63 (16)	C2—N4—H4A	120.0
S2—Cu2—Cu1	122.81 (9)	C2—N4—H4B	120.0
S13—Cu2—Cu1	118.73 (9)	H4A—N4—H4B	120.0
S9—Cu2—Cu1	56.13 (7)	C3—N5—H5A	120.0
S10—Cu2—Cu1	52.16 (13)	C3—N5—H5B	120.0
S3—Cu3—S13	115.16 (12)	H5A—N5—H5B	120.0
S3—Cu3—S12	116.25 (10)	C3—N6—H6A	120.0
S13—Cu3—S12	103.77 (10)	C3—N6—H6B	120.0
S3—Cu3—S11	109.89 (12)	H6A—N6—H6B	120.0
S13—Cu3—S11	101.99 (11)	C4—N7—H7A	120.0
S12—Cu3—S11	108.65 (16)	C4—N7—H7B	120.0
S3—Cu3—Cu4	124.52 (10)	H7A—N7—H7B	120.0
S13—Cu3—Cu4	120.03 (9)	C4—N8—H8A	120.0
S12—Cu3—Cu4	55.39 (7)	C4—N8—H8B	120.0
S11—Cu3—Cu4	53.98 (13)	H8A—N8—H8B	120.0
S4—Cu4—S14	115.22 (12)	C5—N9—H9A	120.0
S4—Cu4—S11	116.02 (10)	C5—N9—H9B	120.0
S14—Cu4—S11	102.36 (10)	H9A—N9—H9B	120.0
S4—Cu4—S12	110.60 (12)	C5—N10—H10A	120.0
S14—Cu4—S12	103.73 (11)	C5—N10—H10B	120.0
S11—Cu4—S12	107.86 (16)	H10A—N10—H10B	120.0
S4—Cu4—Cu3	124.66 (10)	C6—N11—H11A	120.0
S14—Cu4—Cu3	120.03 (9)	C6—N11—H11B	120.0
S11—Cu4—Cu3	55.00 (7)	H11A—N11—H11B	120.0
S12—Cu4—Cu3	53.57 (13)	C6—N12—H12A	120.0
S8—Cu5—S5	120.52 (15)	C6—N12—H12B	120.0
S8—Cu5—S12	104.74 (14)	H12A—N12—H12B	120.0
S5—Cu5—S12	110.78 (11)	C7—N13—H13A	120.0
S8—Cu5—S9	108.14 (14)	C7—N13—H13B	120.0
S5—Cu5—S9	111.07 (12)	H13A—N13—H13B	120.0
S12—Cu5—S9	99.36 (10)	C7—N14—H14A	120.0
S6—Cu6—S7	125.94 (15)	C7—N14—H14B	120.0
S6—Cu6—S10	109.01 (13)	H14A—N14—H14B	120.0
S7—Cu6—S10	106.67 (12)	C8—N15—H15A	120.0
S6—Cu6—S11	110.95 (14)	C8—N15—H15B	120.0
S7—Cu6—S11	99.77 (11)	H15A—N15—H15B	120.0
S10—Cu6—S11	101.72 (11)	C8—N16—H16A	120.0
C1—S1—Cu1	103.0 (4)	C8—N16—H16B	120.0
C2—S2—Cu2	105.7 (4)	H16A—N16—H16B	120.0
C3—S3—Cu3	105.5 (4)	C9—N17—H17A	120.0
C4—S4—Cu4	104.6 (3)	C9—N17—H17B	120.0
C5—S5—Cu5	105.5 (4)	H17A—N17—H17B	120.0
C6—S6—Cu6	112.1 (5)	C9—N18—H18A	120.0
C7—S7—Cu6	108.5 (4)	C9—N18—H18B	120.0
C8—S8—Cu5	112.5 (4)	H18A—N18—H18B	120.0
C9—S9—Cu2	113.2 (4)	C10—N19—H19A	120.0
C9—S9—Cu5	110.7 (3)	C10—N19—H19B	120.0
Cu2—S9—Cu5	119.08 (13)	H19A—N19—H19B	120.0
C9—S9—Cu1	104.2 (3)	C10—N20—H20A	120.0
Cu2—S9—Cu1	71.69 (14)	C10—N20—H20B	120.0
Cu5—S9—Cu1	132.65 (11)	H20A—N20—H20B	120.0
C10—S10—Cu1	114.2 (3)	C11—N21—H21A	120.0
C10—S10—Cu6	112.7 (3)	C11—N21—H21B	120.0
Cu1—S10—Cu6	117.02 (13)	H21A—N21—H21B	120.0
C10—S10—Cu2	107.0 (3)	C11—N22—H22A	120.0
Cu1—S10—Cu2	72.07 (15)	C11—N22—H22B	120.0
Cu6—S10—Cu2	128.04 (11)	H22A—N22—H22B	120.0
C11—S11—Cu4	113.5 (4)	C12—N23—H23A	120.0
C11—S11—Cu6	109.0 (4)	C12—N23—H23B	120.0
Cu4—S11—Cu6	120.88 (13)	H23A—N23—H23B	120.0
C11—S11—Cu3	108.5 (4)	C12—N24—H24A	120.0
Cu4—S11—Cu3	71.02 (14)	C12—N24—H24B	120.0
Cu6—S11—Cu3	129.45 (11)	H24A—N24—H24B	120.0
C12—S12—Cu3	109.9 (4)	C13—N25—H25A	120.0
C12—S12—Cu5	109.0 (4)	C13—N25—H25B	120.0
Cu3—S12—Cu5	117.68 (13)	H25A—N25—H25B	120.0
C12—S12—Cu4	113.0 (4)	C13—N26—H26A	120.0
Cu3—S12—Cu4	71.04 (14)	C13—N26—H26B	120.0
Cu5—S12—Cu4	130.08 (11)	H26A—N26—H26B	120.0
C13—S13—Cu2	106.1 (3)	C14—N27—H27A	120.0
C13—S13—Cu3	105.6 (3)	C14—N27—H27B	120.0
Cu2—S13—Cu3	120.77 (14)	H27A—N27—H27B	120.0
C14—S14—Cu1	106.4 (3)	C14—N28—H28A	120.0
C14—S14—Cu4	105.9 (3)	C14—N28—H28B	120.0
Cu1—S14—Cu4	119.27 (13)	H28A—N28—H28B	120.0
N1—C1—N2	117.9 (11)	O14—Cl1—O11	106.5 (9)
N1—C1—S1	120.7 (10)	O14—Cl1—O13	110.9 (7)
N2—C1—S1	121.3 (8)	O11—Cl1—O13	107.3 (8)
N4—C2—N3	119.0 (10)	O14—Cl1—O12	111.9 (7)
N4—C2—S2	123.0 (8)	O11—Cl1—O12	106.4 (7)
N3—C2—S2	117.7 (9)	O13—Cl1—O12	113.4 (6)
N6—C3—N5	114.9 (9)	O22—Cl2—O23	111.5 (8)
N6—C3—S3	119.2 (9)	O22—Cl2—O24	110.1 (7)
N5—C3—S3	125.9 (8)	O23—Cl2—O24	107.1 (8)
N7—C4—N8	118.1 (10)	O22—Cl2—O21	107.7 (7)
N7—C4—S4	122.9 (8)	O23—Cl2—O21	112.3 (7)
N8—C4—S4	119.0 (8)	O24—Cl2—O21	108.0 (7)
N10—C5—N9	112.6 (12)	O33—Cl3—O31	112.0 (7)
N10—C5—S5	125.7 (9)	O33—Cl3—O32	108.2 (10)
N9—C5—S5	121.7 (8)	O31—Cl3—O32	108.5 (8)
N11—C6—N12	119.0 (10)	O33—Cl3—O34	109.8 (8)
N11—C6—S6	120.0 (10)	O31—Cl3—O34	111.8 (9)
N12—C6—S6	120.9 (9)	O32—Cl3—O34	106.3 (7)
N14—C7—N13	117.6 (10)	O42—Cl4—O44	107.1 (9)
N14—C7—S7	120.1 (9)	O42—Cl4—O43	115.5 (9)
N13—C7—S7	122.3 (8)	O44—Cl4—O43	110.1 (7)
N15—C8—N16	119.3 (9)	O42—Cl4—O41	106.8 (8)
N15—C8—S8	119.8 (10)	O44—Cl4—O41	108.0 (6)
N16—C8—S8	120.9 (8)	O43—Cl4—O41	109.0 (5)
N17—C9—N18	120.1 (9)	O53—Cl5—O52	112.0 (9)
N17—C9—S9	121.5 (8)	O53—Cl5—O51	106.3 (9)
N18—C9—S9	118.4 (8)	O52—Cl5—O51	109.8 (8)
N19—C10—N20	121.2 (9)	O53—Cl5—O54	108.3 (6)
N19—C10—S10	119.3 (8)	O52—Cl5—O54	110.6 (5)
N20—C10—S10	119.4 (7)	O51—Cl5—O54	109.8 (7)
N21—C11—N22	120.5 (10)	O62—Cl6—O61	110.6 (7)
N21—C11—S11	118.6 (9)	O62—Cl6—O64	111.0 (8)
N22—C11—S11	120.6 (8)	O61—Cl6—O64	109.2 (5)
N23—C12—N24	120.4 (9)	O62—Cl6—O63	108.2 (8)
N23—C12—S12	119.7 (8)	O61—Cl6—O63	107.4 (6)
N24—C12—S12	119.9 (8)	O64—Cl6—O63	110.3 (7)

S1—Cu1—Cu2—S2	−17.77 (12)	S7—Cu6—S11—C11	81.4 (4)
S14—Cu1—Cu2—S2	176.98 (12)	S10—Cu6—S11—C11	−169.2 (4)
S10—Cu1—Cu2—S2	86.28 (11)	S6—Cu6—S11—Cu4	172.43 (11)
S9—Cu1—Cu2—S2	−104.29 (11)	S7—Cu6—S11—Cu4	−52.85 (15)
S1—Cu1—Cu2—S13	172.66 (12)	S10—Cu6—S11—Cu4	56.60 (18)
S14—Cu1—Cu2—S13	7.41 (10)	S6—Cu6—S11—Cu3	82.4 (2)
S10—Cu1—Cu2—S13	−83.29 (10)	S7—Cu6—S11—Cu3	−142.91 (17)
S9—Cu1—Cu2—S13	86.14 (10)	S10—Cu6—S11—Cu3	−33.46 (18)
S1—Cu1—Cu2—S9	86.52 (11)	S3—Cu3—S11—C11	9.5 (4)
S14—Cu1—Cu2—S9	−78.74 (11)	S13—Cu3—S11—C11	132.1 (4)
S10—Cu1—Cu2—S9	−169.44 (7)	S12—Cu3—S11—C11	−118.7 (4)
S1—Cu1—Cu2—S10	−104.04 (11)	Cu4—Cu3—S11—C11	−109.3 (4)
S14—Cu1—Cu2—S10	90.70 (11)	S3—Cu3—S11—Cu4	118.82 (11)
S9—Cu1—Cu2—S10	169.44 (7)	S13—Cu3—S11—Cu4	−118.57 (9)
S3—Cu3—Cu4—S4	9.01 (13)	S12—Cu3—S11—Cu4	−9.39 (6)
S13—Cu3—Cu4—S4	−177.50 (12)	S3—Cu3—S11—Cu6	−126.36 (15)
S12—Cu3—Cu4—S4	−91.22 (12)	S13—Cu3—S11—Cu6	−3.75 (17)
S11—Cu3—Cu4—S4	99.61 (12)	S12—Cu3—S11—Cu6	105.42 (15)
S3—Cu3—Cu4—S14	−174.70 (12)	Cu4—Cu3—S11—Cu6	114.82 (16)
S13—Cu3—Cu4—S14	−1.21 (10)	S3—Cu3—S12—C12	−7.0 (4)
S12—Cu3—Cu4—S14	85.07 (11)	S13—Cu3—S12—C12	−134.5 (4)
S11—Cu3—Cu4—S14	−84.10 (11)	S11—Cu3—S12—C12	117.6 (4)
S3—Cu3—Cu4—S11	−90.60 (11)	Cu4—Cu3—S12—C12	108.4 (4)
S13—Cu3—Cu4—S11	82.89 (11)	S3—Cu3—S12—Cu5	118.64 (13)
S12—Cu3—Cu4—S11	169.17 (7)	S13—Cu3—S12—Cu5	−8.86 (14)
S3—Cu3—Cu4—S12	100.23 (11)	S11—Cu3—S12—Cu5	−116.82 (13)
S13—Cu3—Cu4—S12	−86.28 (10)	Cu4—Cu3—S12—Cu5	−126.05 (13)
S11—Cu3—Cu4—S12	−169.17 (7)	S3—Cu3—S12—Cu4	−115.30 (11)
S14—Cu1—S1—C1	−59.6 (4)	S13—Cu3—S12—Cu4	117.19 (9)
S10—Cu1—S1—C1	70.2 (4)	S11—Cu3—S12—Cu4	9.23 (6)
S9—Cu1—S1—C1	−170.5 (4)	S8—Cu5—S12—C12	−63.3 (4)
Cu2—Cu1—S1—C1	134.6 (4)	S5—Cu5—S12—C12	68.1 (4)
S13—Cu2—S2—C2	−48.2 (4)	S9—Cu5—S12—C12	−175.0 (4)
S9—Cu2—S2—C2	76.1 (4)	S8—Cu5—S12—Cu3	170.67 (11)
S10—Cu2—S2—C2	−162.4 (4)	S5—Cu5—S12—Cu3	−57.91 (15)
Cu1—Cu2—S2—C2	142.2 (4)	S9—Cu5—S12—Cu3	58.98 (17)
S13—Cu3—S3—C3	63.8 (4)	S8—Cu5—S12—Cu4	82.9 (2)
S12—Cu3—S3—C3	−57.8 (4)	S5—Cu5—S12—Cu4	−145.73 (16)
S11—Cu3—S3—C3	178.3 (4)	S9—Cu5—S12—Cu4	−28.84 (18)
Cu4—Cu3—S3—C3	−122.4 (4)	S4—Cu4—S12—C12	14.3 (4)
S14—Cu4—S4—C4	61.4 (4)	S14—Cu4—S12—C12	138.4 (4)
S11—Cu4—S4—C4	−58.2 (4)	S11—Cu4—S12—C12	−113.5 (4)
S12—Cu4—S4—C4	178.6 (4)	Cu3—Cu4—S12—C12	−104.2 (4)
Cu3—Cu4—S4—C4	−122.2 (4)	S4—Cu4—S12—Cu3	118.54 (11)
S8—Cu5—S5—C5	−81.0 (4)	S14—Cu4—S12—Cu3	−117.38 (9)
S12—Cu5—S5—C5	156.4 (4)	S11—Cu4—S12—Cu3	−9.31 (6)
S9—Cu5—S5—C5	46.9 (4)	S4—Cu4—S12—Cu5	−130.80 (15)
S7—Cu6—S6—C6	−6.4 (4)	S14—Cu4—S12—Cu5	−6.72 (17)
S10—Cu6—S6—C6	−135.0 (4)	S11—Cu4—S12—Cu5	101.36 (15)
S11—Cu6—S6—C6	113.8 (4)	Cu3—Cu4—S12—Cu5	110.67 (15)
S6—Cu6—S7—C7	−71.7 (4)	S2—Cu2—S13—C13	−55.7 (4)
S10—Cu6—S7—C7	57.9 (4)	S9—Cu2—S13—C13	172.5 (4)
S11—Cu6—S7—C7	163.4 (4)	S10—Cu2—S13—C13	61.0 (4)
S5—Cu5—S8—C8	7.4 (4)	Cu1—Cu2—S13—C13	114.4 (4)
S12—Cu5—S8—C8	133.0 (3)	S2—Cu2—S13—Cu3	−175.49 (11)
S9—Cu5—S8—C8	−121.8 (3)	S9—Cu2—S13—Cu3	52.73 (14)
S2—Cu2—S9—C9	14.3 (3)	S10—Cu2—S13—Cu3	−58.80 (17)
S13—Cu2—S9—C9	145.7 (3)	Cu1—Cu2—S13—Cu3	−5.38 (15)
S10—Cu2—S9—C9	−106.7 (3)	S3—Cu3—S13—C13	56.6 (4)
Cu1—Cu2—S9—C9	−98.0 (3)	S12—Cu3—S13—C13	−175.2 (4)
S2—Cu2—S9—Cu5	−118.45 (13)	S11—Cu3—S13—C13	−62.3 (4)
S13—Cu2—S9—Cu5	12.95 (13)	Cu4—Cu3—S13—C13	−117.4 (4)
S10—Cu2—S9—Cu5	120.50 (12)	S3—Cu3—S13—Cu2	176.73 (11)
Cu1—Cu2—S9—Cu5	129.23 (13)	S12—Cu3—S13—Cu2	−55.09 (14)
S2—Cu2—S9—Cu1	112.32 (10)	S11—Cu3—S13—Cu2	57.78 (17)
S13—Cu2—S9—Cu1	−116.28 (9)	Cu4—Cu3—S13—Cu2	2.65 (16)
S10—Cu2—S9—Cu1	−8.74 (6)	S1—Cu1—S14—C14	−52.2 (4)
S8—Cu5—S9—C9	54.6 (4)	S10—Cu1—S14—C14	173.5 (4)
S5—Cu5—S9—C9	−79.8 (4)	S9—Cu1—S14—C14	61.6 (4)
S12—Cu5—S9—C9	163.6 (4)	Cu2—Cu1—S14—C14	113.5 (4)
S8—Cu5—S9—Cu2	−171.56 (11)	S1—Cu1—S14—Cu4	−171.74 (11)
S5—Cu5—S9—Cu2	54.10 (16)	S10—Cu1—S14—Cu4	53.92 (15)
S12—Cu5—S9—Cu2	−62.57 (17)	S9—Cu1—S14—Cu4	−58.02 (17)
S8—Cu5—S9—Cu1	−80.22 (19)	Cu2—Cu1—S14—Cu4	−6.04 (16)
S5—Cu5—S9—Cu1	145.43 (16)	S4—Cu4—S14—C14	60.0 (4)
S12—Cu5—S9—Cu1	28.77 (18)	S11—Cu4—S14—C14	−173.2 (4)
S1—Cu1—S9—C9	−6.4 (4)	S12—Cu4—S14—C14	−61.0 (4)
S14—Cu1—S9—C9	−128.8 (4)	Cu3—Cu4—S14—C14	−116.6 (4)
S10—Cu1—S9—C9	119.3 (4)	S4—Cu4—S14—Cu1	179.81 (11)
Cu2—Cu1—S9—C9	110.2 (4)	S11—Cu4—S14—Cu1	−53.35 (14)
S1—Cu1—S9—Cu2	−116.63 (10)	S12—Cu4—S14—Cu1	58.79 (18)
S14—Cu1—S9—Cu2	121.04 (9)	Cu3—Cu4—S14—Cu1	3.18 (16)
S10—Cu1—S9—Cu2	9.13 (6)	Cu1—S1—C1—N1	−140.0 (10)
S1—Cu1—S9—Cu5	130.34 (15)	Cu1—S1—C1—N2	36.8 (12)
S14—Cu1—S9—Cu5	8.02 (16)	Cu2—S2—C2—N4	36.0 (12)
S10—Cu1—S9—Cu5	−103.89 (15)	Cu2—S2—C2—N3	−149.7 (11)
Cu2—Cu1—S9—Cu5	−113.02 (16)	Cu3—S3—C3—N6	156.4 (8)
S1—Cu1—S10—C10	8.7 (4)	Cu3—S3—C3—N5	−22.9 (11)
S14—Cu1—S10—C10	143.1 (4)	Cu4—S4—C4—N7	−31.9 (11)
S9—Cu1—S10—C10	−109.8 (4)	Cu4—S4—C4—N8	149.9 (8)
Cu2—Cu1—S10—C10	−101.0 (4)	Cu5—S5—C5—N10	−42.8 (15)
S1—Cu1—S10—Cu6	−126.05 (12)	Cu5—S5—C5—N9	136.2 (12)
S14—Cu1—S10—Cu6	8.29 (14)	Cu6—S6—C6—N11	−178.5 (7)
S9—Cu1—S10—Cu6	115.47 (12)	Cu6—S6—C6—N12	−1.7 (10)
Cu2—Cu1—S10—Cu6	124.19 (13)	Cu6—S7—C7—N14	−155.7 (8)
S1—Cu1—S10—Cu2	109.76 (10)	Cu6—S7—C7—N13	24.5 (11)
S14—Cu1—S10—Cu2	−115.90 (10)	Cu5—S8—C8—N15	178.6 (7)
S9—Cu1—S10—Cu2	−8.72 (6)	Cu5—S8—C8—N16	−0.7 (9)
S6—Cu6—S10—C10	51.3 (4)	Cu2—S9—C9—N17	10.7 (9)
S7—Cu6—S10—C10	−87.4 (4)	Cu5—S9—C9—N17	147.4 (7)
S11—Cu6—S10—C10	168.5 (4)	Cu1—S9—C9—N17	−65.2 (9)
S6—Cu6—S10—Cu1	−173.28 (12)	Cu2—S9—C9—N18	−169.2 (7)
S7—Cu6—S10—Cu1	48.03 (14)	Cu5—S9—C9—N18	−32.5 (8)
S11—Cu6—S10—Cu1	−56.04 (18)	Cu1—S9—C9—N18	114.9 (7)
S6—Cu6—S10—Cu2	−85.56 (19)	Cu1—S10—C10—N19	−166.7 (7)
S7—Cu6—S10—Cu2	135.75 (16)	Cu6—S10—C10—N19	−29.9 (9)
S11—Cu6—S10—Cu2	31.68 (18)	Cu2—S10—C10—N19	115.8 (8)
S2—Cu2—S10—C10	−8.2 (4)	Cu1—S10—C10—N20	17.9 (10)
S13—Cu2—S10—C10	−132.5 (3)	Cu6—S10—C10—N20	154.6 (8)
S9—Cu2—S10—C10	119.8 (3)	Cu2—S10—C10—N20	−59.7 (9)
Cu1—Cu2—S10—C10	110.6 (3)	Cu4—S11—C11—N21	164.7 (10)
S2—Cu2—S10—Cu1	−118.82 (10)	Cu6—S11—C11—N21	26.8 (12)
S13—Cu2—S10—Cu1	116.93 (9)	Cu3—S11—C11—N21	−118.6 (11)
S9—Cu2—S10—Cu1	9.19 (6)	Cu4—S11—C11—N22	−21.8 (11)
S2—Cu2—S10—Cu6	130.50 (14)	Cu6—S11—C11—N22	−159.7 (9)
S13—Cu2—S10—Cu6	6.25 (16)	Cu3—S11—C11—N22	55.0 (11)
S9—Cu2—S10—Cu6	−101.49 (15)	Cu3—S12—C12—N23	141.3 (9)
Cu1—Cu2—S10—Cu6	−110.68 (15)	Cu5—S12—C12—N23	10.9 (11)
S4—Cu4—S11—C11	−13.1 (4)	Cu4—S12—C12—N23	−141.5 (9)
S14—Cu4—S11—C11	−139.4 (4)	Cu3—S12—C12—N24	−40.6 (10)
S12—Cu4—S11—C11	111.6 (4)	Cu5—S12—C12—N24	−171.0 (8)
Cu3—Cu4—S11—C11	102.4 (4)	Cu4—S12—C12—N24	36.6 (10)
S4—Cu4—S11—Cu6	119.23 (14)	Cu2—S13—C13—N25	24.4 (10)
S14—Cu4—S11—Cu6	−7.09 (14)	Cu3—S13—C13—N25	153.7 (9)
S12—Cu4—S11—Cu6	−116.11 (13)	Cu2—S13—C13—N26	−159.6 (9)
Cu3—Cu4—S11—Cu6	−125.25 (14)	Cu3—S13—C13—N26	−30.3 (11)
S4—Cu4—S11—Cu3	−115.52 (11)	Cu1—S14—C14—N27	21.1 (10)
S14—Cu4—S11—Cu3	118.16 (9)	Cu4—S14—C14—N27	149.0 (8)
S12—Cu4—S11—Cu3	9.14 (6)	Cu1—S14—C14—N28	−156.3 (8)
S6—Cu6—S11—C11	−53.4 (4)	Cu4—S14—C14—N28	−28.4 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O43ⁱ	0.86	2.43	3.080 (17)	133
N1—H1A···O33ⁱⁱ	0.86	2.59	3.289 (19)	139
N2—H2A···O43ⁱ	0.86	2.32	2.997 (14)	136
N2—H2A···N14	0.86	2.55	3.125 (15)	125
N2—H2B···S14	0.86	2.74	3.556 (10)	158
N3—H3A···O42	0.86	2.57	3.30 (2)	143
N4—H4A···O41	0.86	2.21	3.068 (13)	177
N4—H4B···S13	0.86	2.67	3.500 (10)	163
N5—H5B···S13	0.86	2.92	3.725 (11)	157
N6—H6A···O31	0.86	2.47	3.153 (15)	137
N6—H6A···O52	0.86	2.55	3.140 (17)	127
N6—H6B···S8ⁱⁱⁱ	0.86	3.00	3.528 (10)	121
N7—H7A···O54^iv	0.86	2.45	3.121 (14)	135
N7—H7B···S14	0.86	2.79	3.624 (9)	164
N8—H8A···O51^iv	0.86	2.16	3.009 (15)	171
N8—H8B···O12^v	0.86	2.60	3.430 (13)	162
N9—H9B···S7^vi	0.86	2.42	3.276 (12)	175
N10—H10B···S9	0.86	2.66	3.422 (12)	149
N11—H11A···O23ⁱⁱ	0.86	2.25	3.000 (16)	146
N12—H12A···O24ⁱⁱ	0.86	2.49	3.270 (16)	152
N12—H12A···O41ⁱⁱ	0.86	2.59	3.177 (14)	126
N12—H12B···S7	0.86	2.72	3.571 (12)	171
N13—H13A···O31ⁱⁱ	0.86	2.11	2.954 (13)	166
N13—H13B···O53ⁱⁱ	0.86	2.40	2.947 (15)	122
N14—H14A···O33ⁱⁱ	0.86	2.22	3.016 (16)	153
N14—H14B···O61	0.86	2.53	3.341 (14)	157
N15—H15A···O62^vi	0.86	2.26	3.078 (16)	160
N16—H16A···O61^vi	0.86	2.31	3.098 (12)	152
N16—H16A···O54^vii	0.86	2.60	3.124 (12)	120
N16—H16B···S5	0.86	2.58	3.439 (10)	173
N17—H17A···O21^vii	0.86	2.23	2.994 (14)	147
N17—H17B···S2	0.86	2.73	3.507 (10)	151
N18—H18A···O21^vii	0.86	2.23	2.991 (14)	147
N18—H18B···S8	0.86	2.64	3.483 (10)	166
N19—H19A···O63^viii	0.86	2.50	3.230 (14)	144
N19—H19B···S6	0.86	2.72	3.565 (10)	167
N20—H20A···O63^viii	0.86	2.25	3.033 (13)	152
N20—H20B···S1	0.86	2.71	3.485 (10)	150
N21—H21A···O64ⁱⁱⁱ	0.86	2.48	3.236 (13)	147
N21—H21A···O43ⁱⁱ	0.86	2.58	3.067 (13)	117
N21—H21B···S6	0.86	2.66	3.507 (11)	168
N22—H22A···O64ⁱⁱⁱ	0.86	2.27	3.075 (13)	155
N22—H22B···O13^v	0.86	2.50	3.070 (15)	124
N23—H23A···O32	0.86	2.61	3.134 (15)	121
N23—H23B···S8	0.86	2.89	3.623 (9)	144
N24—H24A···O22^v	0.86	2.30	3.096 (14)	154
N24—H24B···O13^v	0.86	2.45	3.035 (13)	126
N25—H25A···O12	0.86	2.19	2.981 (13)	154
N25—H25B···S2	0.86	2.73	3.570 (10)	166
N26—H26A···O12	0.86	2.29	3.061 (13)	149
N26—H26B···S3	0.86	2.68	3.519 (9)	166
N27—H27A···S3^vii	0.86	2.97	3.497 (9)	121
N27—H27B···S1	0.86	2.68	3.532 (10)	170
N28—H28A···S2^v	0.86	2.98	3.415 (9)	114
N28—H28B···S4	0.86	2.75	3.594 (11)	167

Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) x, −y+1, z+1/2; (iii) x+1/2, y+1/2, z; (iv) x−1/2, −y+3/2, z+1/2; (v) x−1/2, y+1/2, z; (vi) x, −y+1, z−1/2; (vii) x−1/2, y−1/2, z; (viii) x+1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	[Cu₆(CH₄N₂S)₁₄](ClO₄)₆
M_r	2043.65
Crystal system, space group	Monoclinic, Cc
Temperature (K)	293
a, b, c (Å)	17.229 (2), 15.363 (3), 27.639 (5)
β (°)	93.30 (15)
V (Å³)	7304 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.42
Crystal size (mm)	0.24 × 0.2 × 0.18

Data collection
Diffractometer	Nonius MACH3 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.568, 0.647
No. of measured, independent and observed [I > 2σ(I)] reflections	7120, 6610, 5203
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.110, 1.03
No. of reflections	6610
No. of parameters	829
No. of restraints	4
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0685P)² + 13.3767P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.22, −0.86
Absolute structure	Flack (1983), with how many Friedel pairs
Absolute structure parameter	0.015 (17)

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXTL/PC (Bruker, 2000), SHELXTL/PC and PLATON (Spek, 2003), SHELXL97 (Sheldrick, 1997).

Selected geometric parameters (Å, º) top

Cu1—S9	2.455 (2)	Cu3—S3	2.271 (3)
Cu1—Cu2	2.807 (4)	Cu3—Cu4	2.768 (3)

Cu2—S9—Cu5	119.08 (13)	Cu4—S11—Cu3	71.02 (14)
Cu2—S9—Cu1	71.69 (14)	Cu6—S11—Cu3	129.45 (11)
Cu5—S9—Cu1	132.65 (11)	Cu3—S12—Cu5	117.68 (13)
Cu1—S10—Cu6	117.02 (13)	Cu3—S12—Cu4	71.04 (14)
Cu1—S10—Cu2	72.07 (15)	Cu5—S12—Cu4	130.08 (11)
Cu6—S10—Cu2	128.04 (11)	Cu2—S13—Cu3	120.77 (14)
Cu4—S11—Cu6	120.88 (13)	Cu1—S14—Cu4	119.27 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O43ⁱ	0.86	2.43	3.080 (17)	133
N1—H1A···O33ⁱⁱ	0.86	2.59	3.289 (19)	139
N2—H2A···O43ⁱ	0.86	2.32	2.997 (14)	136
N2—H2A···N14	0.86	2.55	3.125 (15)	125
N2—H2B···S14	0.86	2.74	3.556 (10)	158
N3—H3A···O42	0.86	2.57	3.30 (2)	143
N4—H4A···O41	0.86	2.21	3.068 (13)	177
N4—H4B···S13	0.86	2.67	3.500 (10)	163
N5—H5B···S13	0.86	2.92	3.725 (11)	157
N6—H6A···O31	0.86	2.47	3.153 (15)	137
N6—H6A···O52	0.86	2.55	3.140 (17)	127
N6—H6B···S8ⁱⁱⁱ	0.86	3.00	3.528 (10)	121
N7—H7A···O54^iv	0.86	2.45	3.121 (14)	135
N7—H7B···S14	0.86	2.79	3.624 (9)	164
N8—H8A···O51^iv	0.86	2.16	3.009 (15)	171
N8—H8B···O12^v	0.86	2.60	3.430 (13)	162
N9—H9B···S7^vi	0.86	2.42	3.276 (12)	175
N10—H10B···S9	0.86	2.66	3.422 (12)	149
N11—H11A···O23ⁱⁱ	0.86	2.25	3.000 (16)	146
N12—H12A···O24ⁱⁱ	0.86	2.49	3.270 (16)	152
N12—H12A···O41ⁱⁱ	0.86	2.59	3.177 (14)	126
N12—H12B···S7	0.86	2.72	3.571 (12)	171
N13—H13A···O31ⁱⁱ	0.86	2.11	2.954 (13)	166
N13—H13B···O53ⁱⁱ	0.86	2.40	2.947 (15)	122
N14—H14A···O33ⁱⁱ	0.86	2.22	3.016 (16)	153.4
N14—H14B···O61	0.86	2.53	3.341 (14)	157
N15—H15A···O62^vi	0.86	2.26	3.078 (16)	160
N16—H16A···O61^vi	0.86	2.31	3.098 (12)	152
N16—H16A···O54^vii	0.86	2.60	3.124 (12)	120
N16—H16B···S5	0.86	2.58	3.439 (10)	173
N17—H17A···O21^vii	0.86	2.23	2.994 (14)	147
N17—H17B···S2	0.86	2.73	3.507 (10)	151
N18—H18A···O21^vii	0.86	2.23	2.991 (14)	147
N18—H18B···S8	0.86	2.64	3.483 (10)	166
N19—H19A···O63^viii	0.86	2.50	3.230 (14)	144
N19—H19B···S6	0.86	2.72	3.565 (10)	167
N20—H20A···O63^viii	0.86	2.25	3.033 (13)	152
N20—H20B···S1	0.86	2.71	3.485 (10)	150
N21—H21A···O64ⁱⁱⁱ	0.86	2.48	3.236 (13)	147
N21—H21A···O43ⁱⁱ	0.86	2.58	3.067 (13)	117
N21—H21B···S6	0.86	2.66	3.507 (11)	168
N22—H22A···O64ⁱⁱⁱ	0.86	2.27	3.075 (13)	155
N22—H22B···O13^v	0.86	2.50	3.070 (15)	124
N23—H23A···O32	0.86	2.61	3.134 (15)	121
N23—H23B···S8	0.86	2.89	3.623 (9)	144
N24—H24A···O22^v	0.86	2.30	3.096 (14)	154
N24—H24B···O13^v	0.86	2.45	3.035 (13)	126
N25—H25A···O12	0.86	2.19	2.981 (13)	154
N25—H25B···S2	0.86	2.73	3.570 (10)	166
N26—H26A···O12	0.86	2.29	3.061 (13)	149
N26—H26B···S3	0.86	2.68	3.519 (9)	166
N27—H27A···S3^vii	0.86	2.97	3.497 (9)	121
N27—H27B···S1	0.86	2.68	3.532 (10)	170
N28—H28A···S2^v	0.86	2.98	3.415 (9)	114
N28—H28B···S4	0.86	2.75	3.594 (11)	167

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