(2,2′-Bi­pyridine-κ2N,N′)tetra­kis­(dimethyl sulfoxide-κO)copper(II) bis­(perchlorate)

Iskenderov, T.

doi:10.1107/S1600536813018485

(2,2′-Bipyridine-κ²N,N′)tetrakis(dimethyl sulfoxide-κO)copper(II) bis(perchlorate)

The title compound, [Cu(C₂H₆OS)₄(C₁₀H₈N₂)](ClO₄)₂, contains a Cu^II ion with a distorted octahedral coordination environment, bonded by four O atoms of the monodentate dimethyl sulfoxide ligands and two N atoms of the bidentate chelating 2,2′-bipyridine ligand. The equatorial Cu—N and Cu—O bond lengths are in the range 1.979 (2)-1.998 (3) Å. The axial Cu—O bond distances are 2.365 (2) and 2.394 (2) Å. In the crystal, the complex cations and perchlorate anions are connected by numerous C—H

O hydrogen bonds, which leads to additional stabilization of the structure. The perchlorate anion is disordered over two sets of sites with a 0.716 (3):0.284 (3) occupancy ratio.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536813018485/nr2046sup1.cif Contains datablocks I, New_Global_Publ_Block
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536813018485/nr2046Isup2.hkl Contains datablock I

CCDC reference: 961973

checkCIF report

Key indicators

Single-crystal X-ray study
T = 120 K
Mean (C-C) = 0.005 Å
Disorder in solvent or counterion
R factor = 0.075
wR factor = 0.160
Data-to-parameter ratio = 36.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT202_ALERT_3_C Isotropic non-H Atoms in Anion/Solvent .........          4
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......     56.543
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......     10.119
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      3.909
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.174
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          8
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2
PLAT975_ALERT_2_C Positive Residual Density at 0.69A from O1     .       0.55 eA-3
PLAT976_ALERT_2_C Negative Residual Density at 0.84A from O6     .      -0.44 eA-3

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         10
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ? Do !
PLAT128_ALERT_4_G Note: Alternate Setting of Space-group P21/c   .      P21/n
PLAT180_ALERT_4_G Check Cell Rounding: # of Values Ending with 0 =          3
PLAT244_ALERT_4_G Low   'Solvent' Ueq as Compared to Neighbors of       Cl2_1
PLAT244_ALERT_4_G Low   'Solvent' Ueq as Compared to Neighbors of       Cl2_2
PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ...................         50 %
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          7
            O4  -CU1 -O1  -S1     58.20  0.70   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         11
            N2  -CU1 -O2  -S2    131.60  1.10   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         19
            N1  -CU1 -O3  -S3    166.90  0.50   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         28
            O1  -CU1 -O4  -S4   -166.60  0.50   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         30
            O3  -CU1 -N1  -C1    154.50  0.50   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         35
            O3  -CU1 -N1  -C9    -23.70  0.70   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         39
            O2  -CU1 -N2  -C8     18.00  0.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         44
            O2  -CU1 -N2  -C10    -3.60  1.20   1.555   1.555   1.555   1.555
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........         10
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Cu1     (II)          2.22
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         10
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600       2092

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   9 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  19 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   8 ALERT type 3 Indicator that the structure quality may be low
  15 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

Comment top

2,2'-Bipyridyl (2,2'-bipy) is a well known neutral bidentate ligand which is widely used in coordination chemistry, in particular, for the preparation of mixed ligand complexes (Fritsky et al., 2004; Kanderal et al., 2005). It is also often used in the synthesis of discrete polynuclear complexes in order to prevent formation of coordination polymers by blocking a certain number of vacant sites in the coordination sphere of a metal ion (Fritsky et al., 2006). The title compound was obtained unintentionally during an attempt to synthesize a mixed-ligand complex of Cu^II with pyridine-2-hydroxamic acid in the framework of our project on study of metal complexes of heterocyclic hydroxamic acids (Świątek-Kozłowska et al., 2002; Golenya et al., 2012a). The crystal structure of the title complex has not hitherto been reported.

The title compound, [Cu(C₁₀H₈N₂)(C₂H₆OS)₄](ClO₄)₂, consists of a cationic Cu²⁺ complex and two perchlorate anions (Fig. 1). The central atom is in distorted octahedral environment formed by two nitrogen donor atoms of bidentately coordinated molecule of 2,2'-bipyridine and by four oxygen atoms of dimethyl sulfoxide molecules. The equatorial plane of the coordination polyhedron is consisting of two nitrogen atoms of 2,2'-bipyridyl and two oxygen atoms of two dimethyl sulfoxide ligands. The axial positions are occupied by oxygen atoms of other two dimethyl sulfoxide ligands. The equatorial Cu—N and Cu—O bond lengths are in the range 1.979 (2) – 1.998 (3) Å. The axial Cu—O bond distances are 2.365 (2) Å and 2.394 (2) Å. The coordination bond lengths Cu—N and Cu—O are typical for distorted octahedral Cu^II complexes with the nitrogen and oxygen donors (Fritsky et al., 1998; Świątek-Kozłowska et al., 2000; Sliva et al., 1997). The N2—Cu1—N1 bite angle is decreased to 81.45 (11)°, which is a consequence of the formation of five-membered chelate ring. The C—N and C—C bond lengths in the pyridine rings are normal for 2-substituted pyridine derivatives (Fritsky et al., 2000; Iskenderov et al., 2009; Moroz et al., 2010; Moroz et al., 2012).

In the crystal structure, the complex cations and perchlorate anions are connected by numerous intermolecular C—H···O hydrogen bonds, in which the aromatic and methyl carbon atoms act as donors while the perchlorate oxygen atoms act as acceptors, which contribute to the stabilization of the structure (Fig. 2). There are also stacking interactions between the aromatic rings of the 2,2'-bipyridine molecules belonging to the neighboring complex molecules with shortest non-covalent contacts C(2)···C(6) (-x, 1 - y, -z) = 3.369 (5) and C(4)···C(10) (-x, 1 - y, -z) = 3.390 (5) Å (Fig. 2).

Related literature top

For applications of the 2,2'-bipyridyl ligand, see: Fritsky et al. (2004, 2006); Kanderal et al. (2005). For related structures, see: Fritsky et al. (1998, 2000); Moroz et al. (2010, 2012); Sliva et al. (1997); Świątek-Kozłowska et al. (2000, 2002); Iskenderov et al. (2009); Golenya et al. (2012a). For the synthesis, see: Golenya et al. (2012b).

Experimental top

The title compound was obtained unexpectedly during an attempt to synthesize a mixed-ligand complex of Cu^II with pyridine-2-hydroxamic acid (Golenya et al., 2012b) in aqueous methanol solution. Cu(ClO₄)₂.6H₂O in methanol (0.0370 g, 0.1 mmol) was added to solution of 2,2'-bipyridine (0.156 g, 1 mmol) and pyridine-2-hydroxamic acid (0.069 g, 0.5 mmol) in methanol (7 ml), afterwards the obtained transparent blue solution left for evaporation in the air at ambient temperature. The obtained dry solid residue was dissolved in 5 ml DMSO and set for crystallization by slow diffusion of 2-propanol vapors at room temperature. During 12 h the blue crystals suitable for X-ray analysis were obtained. They were filtered off, washed with 2-propanol and dried in the air. Yield: 73%. Elemental analysis calc. (%) for C₁₈H₃₂Cl₂CuN₂O₁₂S₄: C 29.63; H 4.42; N 3.84; found: C 29.78; H 4.60; N 3.63.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound, with displacement ellipsoids shown at the 40% probability level. Both orientations for the disordered perchlorate anion are shown. H atoms are drawn as spheres of arbitrary radii.
	Fig. 2. Crystal packing of the title compound. Hydrogen bonds are indicated by dashed lines. Only major orientation is shown for the disordered perchlorate anion.

(2,2'-Bipyridine-κ²N,N')tetrakis(dimethyl sulfoxide-κO)copper(II) bis(perchlorate) top

Crystal data top

[Cu(C₂H₆OS)₄(C₁₀H₈N₂)](ClO₄)₂	F(000) = 1508
M_r = 731.14	D_x = 1.580 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2567 reflections
a = 10.8050 (5) Å	θ = 3.0–25.5°
b = 11.6470 (5) Å	µ = 1.21 mm⁻¹
c = 24.5210 (8) Å	T = 120 K
β = 94.984 (5)°	Block, blue
V = 3074.2 (2) Å³	0.33 × 0.23 × 0.12 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	13140 independent reflections
Radiation source: fine-focus sealed tube	6565 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	R_int = 0.074
Detector resolution: 9 pixels mm^-1	θ_max = 36.7°, θ_min = 3.0°
ϕ scans and ω scans with κ offset	h = −13→17
Absorption correction: multi-scan (MULABS; Blessing, 1995)	k = −15→19
T_min = 0.747, T_max = 0.862	l = −40→31
40246 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.075	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.160	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0589P)²] where P = (F_o² + 2F_c²)/3
13140 reflections	(Δ/σ)_max < 0.001
362 parameters	Δρ_max = 1.21 e Å⁻³
10 restraints	Δρ_min = −0.84 e Å⁻³

Crystal data top

[Cu(C₂H₆OS)₄(C₁₀H₈N₂)](ClO₄)₂	V = 3074.2 (2) Å³
M_r = 731.14	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.8050 (5) Å	µ = 1.21 mm⁻¹
b = 11.6470 (5) Å	T = 120 K
c = 24.5210 (8) Å	0.33 × 0.23 × 0.12 mm
β = 94.984 (5)°

Data collection top

Nonius KappaCCD diffractometer	13140 independent reflections
Absorption correction: multi-scan (MULABS; Blessing, 1995)	6565 reflections with I > 2σ(I)
T_min = 0.747, T_max = 0.862	R_int = 0.074
40246 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.075	10 restraints
wR(F²) = 0.160	H-atom parameters constrained
S = 1.07	Δρ_max = 1.21 e Å⁻³
13140 reflections	Δρ_min = −0.84 e Å⁻³
362 parameters

Special details top

Experimental. The C—H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.95(CH), 0.98(CH₃) and U_iso = 1.2 or 1.5 U_eq(parent atom) for CH and CH₃, respectively. One of the perchlorate anions were found to be disordered over two positions with occupancy factors 0.716/0.284. All atoms were refined with anisotropic displacement parameters except the oxygen atoms of the disordered perchlorate which were refined isotropically. Cl—O bond distances and O···O separations of both (minor and major) fractions of the disordered perchlorate anion as well as the ordered perchlorate (as a model) were restrained to have identical values. For each corresponding pair of the oxygen atoms of the disordered perchlorate anion, the isotropic displacement parameters were restrained to have identical values.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(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	Occ. (<1)
Cu1	0.01095 (4)	0.25254 (3)	0.093944 (15)	0.01663 (10)
S1	−0.22872 (8)	0.37353 (8)	0.15620 (4)	0.0260 (2)
S2	−0.10117 (8)	0.03071 (7)	0.13267 (3)	0.02201 (19)
S3	0.02546 (8)	0.21930 (7)	0.22086 (3)	0.02254 (19)
S4	0.24417 (8)	0.03374 (7)	0.06730 (3)	0.02011 (18)
O1	−0.1237 (2)	0.4013 (2)	0.12111 (10)	0.0256 (5)
O2	−0.1282 (2)	0.14612 (18)	0.10375 (9)	0.0185 (5)
O3	0.0926 (2)	0.22831 (19)	0.16856 (9)	0.0224 (5)
O4	0.1196 (2)	0.0936 (2)	0.06162 (9)	0.0225 (5)
Cl1	0.46540 (9)	0.22816 (8)	−0.07645 (4)	0.0300 (2)
O5	0.5215 (3)	0.2784 (3)	−0.12148 (12)	0.0607 (10)
O6	0.3432 (3)	0.2715 (2)	−0.07428 (13)	0.0490 (8)
O7	0.4600 (3)	0.1059 (3)	−0.08316 (15)	0.0599 (10)
O8	0.5387 (3)	0.2541 (3)	−0.02657 (11)	0.0535 (9)
Cl2_1	0.4834 (4)	0.2572 (3)	0.25477 (14)	0.0236 (7)	0.716 (3)
O9_1	0.4557 (4)	0.1434 (3)	0.26534 (16)	0.0426 (10)*	0.716 (3)
O10_1	0.4453 (6)	0.3286 (5)	0.2980 (2)	0.0806 (16)*	0.716 (3)
O11_1	0.6132 (5)	0.2703 (5)	0.2537 (2)	0.0843 (17)*	0.716 (3)
O12_1	0.4289 (5)	0.2943 (4)	0.20296 (19)	0.0643 (13)*	0.716 (3)
Cl2_2	0.4738 (9)	0.2835 (7)	0.2563 (4)	0.0217 (17)	0.284 (3)
O9_2	0.3653 (8)	0.3114 (8)	0.2807 (4)	0.0426 (10)*	0.284 (3)
O10_2	0.5733 (10)	0.2666 (10)	0.2973 (5)	0.0806 (16)*	0.284 (3)
O11_2	0.5087 (11)	0.3809 (9)	0.2254 (5)	0.0843 (17)*	0.284 (3)
O12_2	0.4559 (10)	0.1942 (8)	0.2174 (4)	0.0643 (13)*	0.284 (3)
N1	−0.0439 (2)	0.2824 (2)	0.01530 (11)	0.0165 (6)
N2	0.1453 (2)	0.3611 (2)	0.07722 (10)	0.0169 (6)
C1	−0.1461 (3)	0.2403 (3)	−0.01254 (13)	0.0199 (7)
H1	−0.2011	0.1935	0.0060	0.024*
C2	−0.1736 (3)	0.2635 (3)	−0.06822 (14)	0.0235 (7)
H2	−0.2471	0.2338	−0.0872	0.028*
C3	−0.0930 (3)	0.3302 (3)	−0.09514 (13)	0.0229 (7)
H3	−0.1093	0.3455	−0.1331	0.028*
C4	0.0120 (3)	0.3746 (3)	−0.06631 (13)	0.0227 (8)
H4	0.0682	0.4214	−0.0841	0.027*
C5	0.2357 (3)	0.4606 (3)	0.00510 (14)	0.0251 (8)
H5	0.2326	0.4815	−0.0324	0.030*
C6	0.3321 (4)	0.4966 (3)	0.04112 (15)	0.0292 (9)
H6	0.3967	0.5425	0.0287	0.035*
C7	0.3345 (3)	0.4653 (3)	0.09585 (15)	0.0243 (8)
H7	0.4001	0.4900	0.1215	0.029*
C8	0.2394 (3)	0.3976 (3)	0.11236 (14)	0.0206 (7)
H8	0.2406	0.3762	0.1498	0.025*
C9	0.0340 (3)	0.3495 (3)	−0.01083 (13)	0.0182 (7)
C10	0.1433 (3)	0.3933 (3)	0.02420 (13)	0.0183 (7)
C12	−0.3584 (3)	0.3309 (4)	0.11044 (16)	0.0356 (9)
H12A	−0.3773	0.3915	0.0832	0.053*
H12B	−0.4307	0.3181	0.1312	0.053*
H12C	−0.3382	0.2597	0.0918	0.053*
C13	−0.2864 (4)	0.5103 (4)	0.17568 (17)	0.0423 (11)
H13A	−0.2233	0.5490	0.2003	0.063*
H13B	−0.3620	0.4994	0.1945	0.063*
H13C	−0.3055	0.5575	0.1429	0.063*
C14	−0.1260 (4)	−0.0737 (3)	0.08036 (15)	0.0320 (9)
H14A	−0.2080	−0.0621	0.0608	0.048*
H14B	−0.1217	−0.1506	0.0967	0.048*
H14C	−0.0619	−0.0661	0.0547	0.048*
C15	−0.2366 (4)	0.0083 (4)	0.16771 (16)	0.0364 (10)
H15A	−0.2396	0.0655	0.1969	0.055*
H15B	−0.2342	−0.0689	0.1837	0.055*
H15C	−0.3106	0.0159	0.1419	0.055*
C16	0.0575 (4)	0.3504 (3)	0.25593 (16)	0.0404 (10)
H16A	0.1473	0.3645	0.2591	0.061*
H16B	0.0282	0.3458	0.2926	0.061*
H16C	0.0148	0.4133	0.2355	0.061*
C17	0.1207 (4)	0.1252 (3)	0.26321 (15)	0.0332 (9)
H17A	0.1133	0.0471	0.2485	0.050*
H17B	0.0939	0.1263	0.3004	0.050*
H17C	0.2074	0.1504	0.2642	0.050*
C18	0.2790 (4)	0.0049 (4)	0.13850 (14)	0.0354 (10)
H18A	0.2735	0.0762	0.1593	0.053*
H18B	0.3632	−0.0265	0.1446	0.053*
H18C	0.2192	−0.0509	0.1506	0.053*
C19	0.3605 (3)	0.1404 (3)	0.06048 (17)	0.0324 (9)
H19A	0.3422	0.1819	0.0260	0.049*
H19B	0.4420	0.1034	0.0606	0.049*
H19C	0.3612	0.1944	0.0911	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0172 (2)	0.01757 (19)	0.01494 (18)	−0.00310 (17)	0.00027 (14)	0.00218 (16)
S1	0.0200 (4)	0.0336 (5)	0.0251 (4)	0.0051 (4)	0.0070 (4)	0.0087 (4)
S2	0.0234 (5)	0.0188 (4)	0.0229 (4)	−0.0060 (3)	−0.0037 (3)	0.0044 (3)
S3	0.0262 (5)	0.0238 (4)	0.0173 (4)	−0.0015 (4)	0.0005 (3)	−0.0019 (3)
S4	0.0205 (4)	0.0190 (4)	0.0211 (4)	0.0024 (3)	0.0030 (3)	0.0007 (3)
O1	0.0245 (13)	0.0220 (13)	0.0321 (14)	−0.0021 (10)	0.0139 (11)	−0.0001 (10)
O2	0.0199 (12)	0.0161 (11)	0.0193 (11)	−0.0009 (9)	0.0007 (9)	0.0031 (9)
O3	0.0237 (13)	0.0249 (13)	0.0177 (11)	−0.0068 (10)	−0.0023 (10)	0.0041 (9)
O4	0.0174 (12)	0.0230 (12)	0.0267 (13)	0.0047 (10)	−0.0001 (10)	−0.0016 (10)
Cl1	0.0255 (5)	0.0340 (5)	0.0313 (5)	−0.0103 (4)	0.0071 (4)	−0.0072 (4)
O5	0.0444 (19)	0.113 (3)	0.0248 (15)	−0.0251 (19)	0.0071 (14)	0.0041 (17)
O6	0.0458 (19)	0.0425 (18)	0.061 (2)	0.0143 (15)	0.0204 (16)	0.0078 (15)
O7	0.048 (2)	0.0341 (17)	0.093 (3)	0.0076 (15)	−0.0144 (18)	−0.0270 (17)
O8	0.065 (2)	0.067 (2)	0.0276 (15)	−0.0458 (18)	0.0013 (14)	−0.0026 (15)
Cl2_1	0.0311 (11)	0.0185 (16)	0.0215 (9)	−0.0024 (11)	0.0034 (7)	0.0011 (9)
Cl2_2	0.034 (3)	0.012 (3)	0.020 (2)	0.001 (2)	0.0045 (18)	−0.0071 (19)
N1	0.0179 (14)	0.0133 (13)	0.0187 (13)	0.0033 (10)	0.0034 (11)	0.0018 (10)
N2	0.0151 (14)	0.0166 (13)	0.0190 (13)	0.0013 (11)	0.0016 (11)	−0.0001 (11)
C1	0.0211 (17)	0.0176 (16)	0.0206 (16)	0.0023 (14)	−0.0009 (13)	−0.0018 (13)
C2	0.0243 (18)	0.0236 (18)	0.0217 (16)	0.0047 (15)	−0.0028 (14)	−0.0014 (14)
C3	0.032 (2)	0.0213 (17)	0.0151 (16)	0.0091 (15)	0.0024 (14)	−0.0009 (13)
C4	0.034 (2)	0.0160 (16)	0.0196 (17)	0.0054 (14)	0.0092 (15)	0.0030 (13)
C5	0.031 (2)	0.0203 (18)	0.0255 (18)	−0.0012 (15)	0.0129 (16)	0.0001 (14)
C6	0.030 (2)	0.0202 (18)	0.040 (2)	−0.0052 (15)	0.0146 (18)	−0.0044 (16)
C7	0.0159 (17)	0.0197 (17)	0.037 (2)	−0.0009 (14)	0.0004 (15)	−0.0044 (15)
C8	0.0163 (17)	0.0185 (16)	0.0262 (17)	0.0007 (13)	−0.0024 (14)	−0.0016 (14)
C9	0.0206 (17)	0.0161 (15)	0.0188 (16)	0.0069 (13)	0.0071 (13)	0.0006 (13)
C10	0.0228 (18)	0.0118 (15)	0.0212 (16)	0.0025 (13)	0.0056 (13)	0.0009 (12)
C12	0.020 (2)	0.049 (3)	0.038 (2)	0.0017 (18)	0.0040 (17)	−0.0008 (19)
C13	0.036 (2)	0.053 (3)	0.039 (2)	0.017 (2)	0.0120 (19)	−0.005 (2)
C14	0.036 (2)	0.0224 (19)	0.037 (2)	−0.0001 (17)	−0.0006 (18)	−0.0047 (16)
C15	0.041 (2)	0.042 (2)	0.027 (2)	−0.0163 (19)	0.0094 (18)	0.0057 (17)
C16	0.054 (3)	0.034 (2)	0.032 (2)	−0.004 (2)	−0.004 (2)	−0.0119 (18)
C17	0.033 (2)	0.044 (2)	0.0229 (18)	0.0091 (19)	0.0058 (16)	0.0110 (17)
C18	0.032 (2)	0.049 (3)	0.0256 (19)	0.0172 (19)	0.0033 (17)	0.0146 (17)
C19	0.024 (2)	0.0237 (19)	0.050 (2)	0.0020 (16)	0.0091 (18)	0.0023 (17)

Geometric parameters (Å, º) top

Cu1—O2	1.979 (2)	C3—C4	1.384 (5)
Cu1—O3	1.981 (2)	C3—H3	0.9500
Cu1—N2	1.994 (3)	C4—C9	1.392 (4)
Cu1—N1	1.998 (3)	C4—H4	0.9500
Cu1—O4	2.365 (2)	C5—C6	1.371 (5)
Cu1—O1	2.394 (2)	C5—C10	1.383 (4)
S1—O1	1.517 (2)	C5—H5	0.9500
S1—C12	1.788 (4)	C6—C7	1.389 (5)
S1—C13	1.791 (4)	C6—H6	0.9500
S2—O2	1.536 (2)	C7—C8	1.384 (5)
S2—C14	1.771 (4)	C7—H7	0.9500
S2—C15	1.779 (4)	C8—H8	0.9500
S3—O3	1.531 (2)	C9—C10	1.488 (5)
S3—C16	1.772 (4)	C12—H12A	0.9800
S3—C17	1.775 (4)	C12—H12B	0.9800
S4—O4	1.512 (2)	C12—H12C	0.9800
S4—C19	1.785 (4)	C13—H13A	0.9800
S4—C18	1.786 (4)	C13—H13B	0.9800
Cl1—O6	1.419 (3)	C13—H13C	0.9800
Cl1—O5	1.430 (3)	C14—H14A	0.9800
Cl1—O8	1.431 (3)	C14—H14B	0.9800
Cl1—O7	1.435 (3)	C14—H14C	0.9800
Cl2_1—O9_1	1.388 (5)	C15—H15A	0.9800
Cl2_1—O11_1	1.413 (7)	C15—H15B	0.9800
Cl2_1—O12_1	1.421 (6)	C15—H15C	0.9800
Cl2_1—O10_1	1.436 (6)	C16—H16A	0.9800
Cl2_2—O9_2	1.399 (9)	C16—H16B	0.9800
Cl2_2—O12_2	1.413 (8)	C16—H16C	0.9800
Cl2_2—O10_2	1.421 (10)	C17—H17A	0.9800
Cl2_2—O11_2	1.432 (9)	C17—H17B	0.9800
N1—C1	1.340 (4)	C17—H17C	0.9800
N1—C9	1.351 (4)	C18—H18A	0.9800
N2—C8	1.343 (4)	C18—H18B	0.9800
N2—C10	1.352 (4)	C18—H18C	0.9800
C1—C2	1.398 (5)	C19—H19A	0.9800
C1—H1	0.9500	C19—H19B	0.9800
C2—C3	1.377 (5)	C19—H19C	0.9800
C2—H2	0.9500

O2—Cu1—O3	94.62 (9)	C6—C5—C10	119.1 (3)
O2—Cu1—N2	174.98 (10)	C6—C5—H5	120.5
O3—Cu1—N2	90.37 (10)	C10—C5—H5	120.5
O2—Cu1—N1	93.53 (10)	C5—C6—C7	119.5 (3)
O3—Cu1—N1	170.76 (10)	C5—C6—H6	120.3
N2—Cu1—N1	81.45 (11)	C7—C6—H6	120.3
O2—Cu1—O4	87.42 (8)	C8—C7—C6	118.7 (3)
O3—Cu1—O4	90.21 (9)	C8—C7—H7	120.6
N2—Cu1—O4	92.05 (9)	C6—C7—H7	120.6
N1—Cu1—O4	85.81 (9)	N2—C8—C7	122.2 (3)
O2—Cu1—O1	86.15 (8)	N2—C8—H8	118.9
O3—Cu1—O1	94.52 (9)	C7—C8—H8	118.9
N2—Cu1—O1	93.98 (9)	N1—C9—C4	121.6 (3)
N1—Cu1—O1	90.35 (9)	N1—C9—C10	114.9 (3)
O4—Cu1—O1	172.30 (8)	C4—C9—C10	123.5 (3)
O1—S1—C12	106.68 (17)	N2—C10—C5	122.1 (3)
O1—S1—C13	104.87 (17)	N2—C10—C9	113.9 (3)
C12—S1—C13	98.2 (2)	C5—C10—C9	124.0 (3)
O2—S2—C14	104.83 (16)	S1—C12—H12A	109.5
O2—S2—C15	102.73 (17)	S1—C12—H12B	109.5
C14—S2—C15	99.78 (19)	H12A—C12—H12B	109.5
O3—S3—C16	105.11 (17)	S1—C12—H12C	109.5
O3—S3—C17	103.87 (15)	H12A—C12—H12C	109.5
C16—S3—C17	99.7 (2)	H12B—C12—H12C	109.5
O4—S4—C19	107.37 (15)	S1—C13—H13A	109.5
O4—S4—C18	106.68 (16)	S1—C13—H13B	109.5
C19—S4—C18	97.6 (2)	H13A—C13—H13B	109.5
S1—O1—Cu1	120.43 (13)	S1—C13—H13C	109.5
S2—O2—Cu1	119.24 (13)	H13A—C13—H13C	109.5
S3—O3—Cu1	125.31 (14)	H13B—C13—H13C	109.5
S4—O4—Cu1	142.59 (14)	S2—C14—H14A	109.5
O6—Cl1—O5	110.0 (2)	S2—C14—H14B	109.5
O6—Cl1—O8	109.9 (2)	H14A—C14—H14B	109.5
O5—Cl1—O8	109.46 (18)	S2—C14—H14C	109.5
O6—Cl1—O7	109.21 (19)	H14A—C14—H14C	109.5
O5—Cl1—O7	109.5 (2)	H14B—C14—H14C	109.5
O8—Cl1—O7	108.8 (2)	S2—C15—H15A	109.5
O9_1—Cl2_1—O11_1	109.7 (4)	S2—C15—H15B	109.5
O9_1—Cl2_1—O12_1	112.2 (3)	H15A—C15—H15B	109.5
O11_1—Cl2_1—O12_1	106.6 (4)	S2—C15—H15C	109.5
O9_1—Cl2_1—O10_1	109.6 (3)	H15A—C15—H15C	109.5
O11_1—Cl2_1—O10_1	107.4 (4)	H15B—C15—H15C	109.5
O12_1—Cl2_1—O10_1	111.2 (4)	S3—C16—H16A	109.5
O9_2—Cl2_2—O12_2	112.9 (7)	S3—C16—H16B	109.5
O9_2—Cl2_2—O10_2	109.9 (7)	H16A—C16—H16B	109.5
O12_2—Cl2_2—O10_2	115.2 (8)	S3—C16—H16C	109.5
O9_2—Cl2_2—O11_2	108.1 (7)	H16A—C16—H16C	109.5
O12_2—Cl2_2—O11_2	104.7 (7)	H16B—C16—H16C	109.5
O10_2—Cl2_2—O11_2	105.4 (7)	S3—C17—H17A	109.5
C1—N1—C9	119.4 (3)	S3—C17—H17B	109.5
C1—N1—Cu1	126.2 (2)	H17A—C17—H17B	109.5
C9—N1—Cu1	114.4 (2)	S3—C17—H17C	109.5
C8—N2—C10	118.5 (3)	H17A—C17—H17C	109.5
C8—N2—Cu1	126.3 (2)	H17B—C17—H17C	109.5
C10—N2—Cu1	115.0 (2)	S4—C18—H18A	109.5
N1—C1—C2	121.5 (3)	S4—C18—H18B	109.5
N1—C1—H1	119.2	H18A—C18—H18B	109.5
C2—C1—H1	119.2	S4—C18—H18C	109.5
C3—C2—C1	119.2 (3)	H18A—C18—H18C	109.5
C3—C2—H2	120.4	H18B—C18—H18C	109.5
C1—C2—H2	120.4	S4—C19—H19A	109.5
C2—C3—C4	119.4 (3)	S4—C19—H19B	109.5
C2—C3—H3	120.3	H19A—C19—H19B	109.5
C4—C3—H3	120.3	S4—C19—H19C	109.5
C3—C4—C9	118.9 (3)	H19A—C19—H19C	109.5
C3—C4—H4	120.5	H19B—C19—H19C	109.5
C9—C4—H4	120.5

C12—S1—O1—Cu1	−85.9 (2)	O1—Cu1—N1—C9	98.2 (2)
C13—S1—O1—Cu1	170.58 (18)	O2—Cu1—N2—C8	−179 (55)
O2—Cu1—O1—S1	24.70 (16)	O3—Cu1—N2—C8	−4.9 (3)
O3—Cu1—O1—S1	−69.64 (17)	N1—Cu1—N2—C8	179.4 (3)
N2—Cu1—O1—S1	−160.33 (17)	O4—Cu1—N2—C8	−95.1 (3)
N1—Cu1—O1—S1	118.21 (17)	O1—Cu1—N2—C8	89.7 (3)
O4—Cu1—O1—S1	58.2 (7)	O2—Cu1—N2—C10	−3.6 (12)
C14—S2—O2—Cu1	−109.80 (17)	O3—Cu1—N2—C10	170.5 (2)
C15—S2—O2—Cu1	146.32 (17)	N1—Cu1—N2—C10	−5.2 (2)
O3—Cu1—O2—S2	−42.44 (15)	O4—Cu1—N2—C10	80.2 (2)
N2—Cu1—O2—S2	131.6 (11)	O1—Cu1—N2—C10	−95.0 (2)
N1—Cu1—O2—S2	133.21 (15)	C9—N1—C1—C2	0.4 (5)
O4—Cu1—O2—S2	47.57 (14)	Cu1—N1—C1—C2	−177.8 (2)
O1—Cu1—O2—S2	−136.67 (15)	N1—C1—C2—C3	0.8 (5)
C16—S3—O3—Cu1	−106.8 (2)	C1—C2—C3—C4	−1.3 (5)
C17—S3—O3—Cu1	148.92 (19)	C2—C3—C4—C9	0.7 (5)
O2—Cu1—O3—S3	−41.26 (17)	C10—C5—C6—C7	−0.3 (5)
N2—Cu1—O3—S3	139.26 (17)	C5—C6—C7—C8	0.5 (5)
N1—Cu1—O3—S3	166.9 (5)	C10—N2—C8—C7	−0.9 (5)
O4—Cu1—O3—S3	−128.69 (16)	Cu1—N2—C8—C7	174.3 (2)
O1—Cu1—O3—S3	45.24 (17)	C6—C7—C8—N2	0.1 (5)
C19—S4—O4—Cu1	−49.5 (3)	C1—N1—C9—C4	−1.1 (4)
C18—S4—O4—Cu1	54.3 (3)	Cu1—N1—C9—C4	177.3 (2)
O2—Cu1—O4—S4	−133.1 (2)	C1—N1—C9—C10	179.0 (3)
O3—Cu1—O4—S4	−38.5 (2)	Cu1—N1—C9—C10	−2.7 (3)
N2—Cu1—O4—S4	51.9 (2)	C3—C4—C9—N1	0.5 (5)
N1—Cu1—O4—S4	133.1 (2)	C3—C4—C9—C10	−179.5 (3)
O1—Cu1—O4—S4	−166.6 (5)	C8—N2—C10—C5	1.1 (5)
O2—Cu1—N1—C1	2.6 (3)	Cu1—N2—C10—C5	−174.6 (2)
O3—Cu1—N1—C1	154.5 (5)	C8—N2—C10—C9	−179.1 (3)
N2—Cu1—N1—C1	−177.5 (3)	Cu1—N2—C10—C9	5.2 (3)
O4—Cu1—N1—C1	89.8 (3)	C6—C5—C10—N2	−0.5 (5)
O1—Cu1—N1—C1	−83.5 (3)	C6—C5—C10—C9	179.7 (3)
O2—Cu1—N1—C9	−175.6 (2)	N1—C9—C10—N2	−1.6 (4)
O3—Cu1—N1—C9	−23.7 (7)	C4—C9—C10—N2	178.4 (3)
N2—Cu1—N1—C9	4.2 (2)	N1—C9—C10—C5	178.1 (3)
O4—Cu1—N1—C9	−88.5 (2)	C4—C9—C10—C5	−1.8 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2	0.95	2.52	3.046 (4)	115
C6—H6···O8ⁱ	0.95	2.47	3.255 (5)	140
C8—H8···O3	0.95	2.42	2.946 (4)	115
C4—H4···O1ⁱⁱ	0.95	2.35	3.219 (4)	151
C16—H16B···O5ⁱⁱⁱ	0.98	2.56	3.411 (5)	145
C17—H17B···O5ⁱⁱⁱ	0.98	2.40	3.306 (5)	153
C15—H15C···O7^iv	0.98	2.51	3.320 (5)	140

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

Experimental details

Crystal data
Chemical formula	[Cu(C₂H₆OS)₄(C₁₀H₈N₂)](ClO₄)₂
M_r	731.14
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	10.8050 (5), 11.6470 (5), 24.5210 (8)
β (°)	94.984 (5)
V (Å³)	3074.2 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.21
Crystal size (mm)	0.33 × 0.23 × 0.12

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (MULABS; Blessing, 1995)
T_min, T_max	0.747, 0.862
No. of measured, independent and observed [I > 2σ(I)] reflections	40246, 13140, 6565
R_int	0.074
(sin θ/λ)_max (Å⁻¹)	0.840

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.075, 0.160, 1.07
No. of reflections	13140
No. of parameters	362
No. of restraints	10
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.21, −0.84

Computer programs: COLLECT (Nonius, 2000), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2009).