Bis(μ2-4,7-dimethyl-4,7-diazadecane-1,10-dithiolato)trinickel(II) bis(perchlorate)

Hirotsu, M.; Kuwamura, N.; Kinoshita, I.; Kojima, M.; Yoshikawa, Y.

doi:10.1107/S1600536812006034

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page m307

doi:10.1107/S1600536812006034

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Bis(μ₂-4,7-dimethyl-4,7-diazadecane-1,10-dithiolato)trinickel(II) bis(perchlorate)

Masakazu Hirotsu,^a ^* Naoto Kuwamura,^a Isamu Kinoshita,^a Masaaki Kojima ^b and Yuzo Yoshikawa ^b

^aGraduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan, and ^bDepartment of Chemistry, Faculty of Science, Okayama University, Tsushima, Okayama 700-8530, Japan
^*Correspondence e-mail: mhiro@sci.osaka-cu.ac.jp

(Received 16 January 2012; accepted 10 February 2012; online 17 February 2012)

In the title compound, [Ni₃(C₁₀H₂₂N₂S₂)₂](ClO₄)₂, the complex cation consists of a nickel(II) ion and two [Ni(C₁₀H₂₂N₂S₂)] units with an N₂S₂ tetradentate ligand, 3,3′-[1,2-ethanediylbis(methylimino)]bis(1-propanethiolate). The central Ni^II ion is located on a crystallographic inversion centre and is bound to the four S atoms of the two [Ni(C₁₀H₂₂N₂S₂)] units to form a linear sulfur-bridged trimetallic moiety. The dihedral angle between the central NiS₄ plane and the terminal NiN₂S₂ plane is 145.71 (5)°. In the [Ni(C₁₀H₂₂N₂S₂)] unit, the two methyl groups on the chelating N atoms are cis to each other, and the two six-membered N,S-chelate rings adopt a chair conformation. The Ni—S bond lengths and the S—Ni—S bite angles in the central NiS₄ group are similar to those in the [Ni(C₁₀H₂₂N₂S₂)] unit.

Related literature

For general background, see: Konno et al. (2000 ); Konno (2004 ); Igashira-Kamiyama & Konno (2011 ). For related structures, see: Grapperhaus et al. (2007 ); Turner et al. (1990 ).

Experimental

Crystal data

[Ni₃(C₁₀H₂₂N₂S₂)₂](ClO₄)₂
M_r = 843.83
Monoclinic, P 2₁ /c
a = 8.0253 (19) Å
b = 16.208 (4) Å
c = 12.807 (3) Å
β = 105.033 (6)°
V = 1608.8 (7) Å³
Z = 2
Mo Kα radiation
μ = 2.21 mm⁻¹
T = 123 K
0.24 × 0.24 × 0.17 mm

Data collection

Rigaku AFC7 (Mercury CCD) diffractometer
Absorption correction: multi-scan (REQAB; Jacobson 1998 ) T_min = 0.619, T_max = 0.705
15030 measured reflections
3626 independent reflections
3391 reflections with F² > 2.0σ(F²)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.082
S = 1.04
3626 reflections
235 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.71 e Å⁻³
Δρ_min = −0.70 e Å⁻³

Data collection: CrystalClear (Rigaku, 2007 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812006034/fj2508sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812006034/fj2508Isup2.hkl

checkCIF report

Comment top

Thiolate ligands have a high propensity to bridge transition metal ions and form sulfur-bridged polynuclear metal complexes. Metal complexes of polydentate ligands with thiolato-S atoms were used to construct supramolecular compounds (Konno et al., 2000; Konno, 2004; Igashira-Kamiyama & Konno, 2011). Nickel(II) complexes containing diamine dithiolate ligands act as a bidentate-S,S metalloligand. The title compound [Ni{Ni(C₁₀H₂₂N₂S₂)}₂](ClO₄)₂, (I), was synthesized by the reaction of 3,3'-[1,2-ethanediylbis(methylimino)]bis(1-propanethiol) with nickel(II) acetate tetrahydrate. The corresponding mononuclear nickel(II) complex [Ni(C₁₀H₂₂N₂S₂)], (II), which has a five-membered N,N- and two six-membered N,S-chelate rings, was synthesized and structurally characterized (Grapperhaus et al., 2007). On the other hand, a mononuclear nickel(II) complex of 2,2'-[1,2-ethanediylbis(methylimino)]bis(ethanethiolate) (L), [Ni(L)], reacts with nickel(II) chloride to afford a sulfur-bridged trinuclear complex, [Ni{Ni(L)}₂]Cl₂, (III), in which the S,N,N,S-tetradentate ligand L forms five-membered N,N- and N,S-chelate rings (Turner et al., 1990). The trinuclear complex (III) has a chair structure consisting of a central NiS₄ and two terminal NiN₂S₂ planes, where the dihedral angle between the NiS₄ and NiN₂S₂ planes is 107.84 (7)°. In this report, we discuss the structure of the new S-bridged Ni^II₃ complex (I), in which the size of the N,S-chelate rings is larger than that of (III).

The title compound (I) is composed of a complex cation, [Ni{Ni(C₁₀H₂₂N₂S₂)}₂]²⁺, containing two N₂S₂ tetradentate ligands, 3,3'-[1,2-ethanediylbis(methylimino)]bis(1-propanethiolate), and two perchlorate anions (Fig. 1). The complex cation consists of a nickel(II) ion and two mononuclear [Ni(C₁₀H₂₂N₂S₂)] complex units, and the overall structure is similar to that of (III). The central Ni atom is located on a crystallographic inversion center and is surrounded by four S atoms of the two planar [Ni(C₁₀H₂₂N₂S₂)] units. The NiS₄ structure is also planar. The structural parameters of the [Ni(C₁₀H₂₂N₂S₂)] unit in (I) are quite similar to those of the mononuclear complex (II). However, two methyl groups on the chelating N atoms of (I) are in a cis position to each other, while those of (II) are in a trans position. The dihedral angle between the NiS₄ and NiN₂S₂ planes is 145.71 (5)°, which is significantly larger than that of (III) with five-membered N,S-chelate rings. Furthermore, the Ni—S—Ni angles (92.46 (3)°, 92.32 (2)°) and the Ni···Ni distance (3.1518 (6) Å) in (I) are larger than those in (III) (77.71 (4)°, 78.10 (4)°, 2.748 (1) Å). These results suggest that the chelate ring size of polydentate thiolate ligands largely affects the structure of S-bridged polynuclear metal complexes.

Related literature top

For general background, see: Konno et al. (2000); Konno (2004); Igashira-Kamiyama & Konno (2011). For related structures, see: Grapperhaus et al. (2007); Turner et al. (1990).

Experimental top

For the preparation of 3,3'-[1,2-ethanediylbis(methylimino)]bis(1-propanol), a solution of 3-bromo-1-propanol (11.66 g, 84 mmol) in CH₂Cl₂ (30 ml) was added dropwise to a solution of N,N'-dimethylethylenediamine (3.53 g, 40 mmol) and N,N-diisopropylethylamine (10.83 g, 84 mmol) in CH₂Cl₂ (20 ml). The solution was stirred for 31 h at room temperature. An aqueous solution of NaOH (4 mol dm^-3, 50 ml) was added. The product was extracted with CH₂Cl₂ (300 ml). After removing the solvent, distillation under reduced pressure gave a colorless oil of 3,3'-[1,2-ethanediylbis(methylimino)]bis(1-propanol) (2.85 g, 35%). ¹H NMR (270 MHz, CDCl₃) δ 1.58–1.68 (m, 4H), 2.18 (s, 6H, CH₃), 2.43 (s, 4H, NCH₂CH₂N), 2.49 (t, J = 6.3 Hz, 4H), 3.67 (t, J = 5.4 Hz, 4H), 5.20 (s, br, 2H).

For the preparation of 3,3'-[1,2-ethanediylbis(methylimino)]bis(1-propanethiol), a mixture of 3,3'-[1,2-ethanediylbis(methylimino)]bis(1-propanol) (0.82 g, 4.0 mmol), 47% HBr aq. (11 ml, 103 mmol), and thiourea (0.76 g, 10 mmol) was refluxed for 24 h. An aqueous solution of NaOH (2.5 mol dm^-3, 52 ml) was added under N₂, and the suspension was refluxed for 5 h under N₂. The produced oil was extracted with diethyl ether (100 ml). The solution was adjusted to pH 8–9 with an aqueous HCl solution (2 mol dm^-3), and the product was extracted with diethyl ether (200 ml). The combined extracts were dried over Na₂SO₄, and the solvent was removed by evaporation to afford a pale yellow oil (0.77 g, 81%). ¹H NMR (270 MHz, CDCl₃) δ 1.70–1.82 (m, 4H), 2.21 (s, 6H, CH₃), 2.45 (s, 4H, NCH₂CH₂N), 2.39–2.58 (m, 8H).

For the synthesis of the title compound (I), a solution of 3,3'-[1,2-ethanediylbis(methylimino)]bis(1-propanethiol) (0.71 g, 3.0 mmol) in methanol (10 ml) was added to a suspension of nickel(II) acetate tetrahydrate (1.50 g, 6.0 mmol) in methanol (20 ml). The resulting dark brown suspension was stirred for 5 min, and then sodium perchlorate monohydrate (0.85 g, 6.0 mmol) was added. After stirring for 30 min, brown precipitate was filtered and washed with MeOH, H₂O, and then MeOH. The brown solid of (I) was dried under reduced pressure over P₄O₁₀ (0.44 g, 35%). Red crystals suitable for X-ray analysis were obtained by heating a solution of (I) in N,N-dimethylformamide (DMF). Anal. Calcd for C₂₀H₄₄Cl₂N₄Ni₃O₈S₄: C, 28.47; H, 5.26; N, 6.64%. Found: C, 28.63; H, 5.03; N, 6.68%. ¹H NMR (300 MHz, dimethylsulfoxide-d₆): δ 1.41–1.70 (m, br, 8H), 1.87–2.03 (m, br, 4H), 2.07–2.29 (m, br, 4H), 2.36–2.48 (m, br, 4H), 2.46 (s, 12H, CH₃), 2.59–2.86 (m, br, 8H), 3.47–3.66 (m, br, 4H). ¹³C NMR (75.5 MHz, dimethylsulfoxide-d₆): δ 24.0, 26.0, 45.3, 58.7, 60.1. UV-Vis (DMF): λ/nm (ε/dm³ mol^-1 cm^-1), 334 (14800), 397 (8730), 480 (1900, sh). Cyclic voltammogram (solvent, DMF; concentration, 5.0 × 10 ^-4 mol dm^-3; supporting electrolyte, 0.1 mol dm^-3 Bu₄NPF₆; working electrode, 0.02 cm² Pt disk electrode; scan rate, 100 mV/s): E/V (versus ferrocenium/ferrocene); E_pc, -1.95 (i_pc = 1.7 µA); E_1/2, -1.59 (ΔE_p = 69 mV, i_pa/i_pc = 0.59, i_pc = 1.6 µA).

Computing details top

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and publCIF (Westrip, 2010).

Figures top

Fig. 1. The molecular structure of (I) with numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Bis(µ₂-4,7-dimethyl-4,7-diazadecane-1,10-dithiolato)trinickel(II) bis(perchlorate) top

Crystal data top

[Ni₃(C₁₀H₂₂N₂S₂)₂](ClO₄)₂	F(000) = 876.00
M_r = 843.83	D_x = 1.742 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 7222 reflections
a = 8.0253 (19) Å	θ = 4.1–27.5°
b = 16.208 (4) Å	µ = 2.21 mm⁻¹
c = 12.807 (3) Å	T = 123 K
β = 105.033 (6)°	Prism, red
V = 1608.8 (7) Å³	0.24 × 0.24 × 0.17 mm
Z = 2

Data collection top

Rigaku AFC7 (Mercury CCD) diffractometer	3626 independent reflections
Radiation source: rotating anode X-ray tube	3391 reflections with F² > 2.0σ(F²)
Graphite monochromator	R_int = 0.027
Detector resolution: 7.31 pixels mm^-1	θ_max = 27.5°, θ_min = 4.1°
ω scans	h = −10→10
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −21→20
T_min = 0.619, T_max = 0.705	l = −13→16
15030 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.035	w = 1/[σ²(F_o²) + (0.0319P)² + 3.9221P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.082	(Δ/σ)_max = 0.002
S = 1.04	Δρ_max = 1.71 e Å⁻³
3626 reflections	Δρ_min = −0.70 e Å⁻³
235 parameters

Crystal data top

[Ni₃(C₁₀H₂₂N₂S₂)₂](ClO₄)₂	V = 1608.8 (7) Å³
M_r = 843.83	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.0253 (19) Å	µ = 2.21 mm⁻¹
b = 16.208 (4) Å	T = 123 K
c = 12.807 (3) Å	0.24 × 0.24 × 0.17 mm
β = 105.033 (6)°

Data collection top

Rigaku AFC7 (Mercury CCD) diffractometer	3626 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	3391 reflections with F² > 2.0σ(F²)
T_min = 0.619, T_max = 0.705	R_int = 0.027
15030 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 1.71 e Å⁻³
3626 reflections	Δρ_min = −0.70 e Å⁻³
235 parameters

Special details top

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ni1	0.04531 (4)	0.626726 (19)	0.82272 (2)	0.01439 (10)
Ni2	0.0000	0.5000	1.0000	0.01306 (11)
Cl1	0.28814 (8)	0.39140 (4)	0.71998 (5)	0.02463 (15)
S1	−0.16594 (8)	0.55517 (4)	0.85310 (5)	0.01655 (13)
S2	0.14612 (8)	0.61385 (4)	0.99699 (5)	0.01539 (13)
O1	0.2236 (4)	0.4191 (2)	0.8082 (2)	0.0720 (11)
O2	0.4299 (3)	0.33683 (14)	0.76150 (19)	0.0357 (5)
O3	0.1505 (3)	0.35038 (17)	0.64509 (18)	0.0431 (6)
O4	0.3425 (4)	0.46058 (19)	0.6684 (3)	0.0680 (10)
N1	−0.0478 (3)	0.63136 (14)	0.66462 (17)	0.0224 (5)
N2	0.2398 (3)	0.69848 (15)	0.80846 (18)	0.0228 (5)
C1	−0.2110 (4)	0.47418 (18)	0.7507 (2)	0.0241 (6)
C2	−0.2552 (4)	0.5093 (2)	0.6370 (2)	0.0286 (6)
C3	−0.1047 (4)	0.55199 (17)	0.6077 (2)	0.0222 (5)
C4	0.3641 (3)	0.57575 (18)	1.0035 (2)	0.0212 (5)
C5	0.4731 (4)	0.63872 (18)	0.9633 (2)	0.0225 (5)
C6	0.4124 (3)	0.65719 (17)	0.8436 (2)	0.0202 (5)
C7	0.1093 (5)	0.6568 (3)	0.6256 (3)	0.0433 (9)
C8	0.2043 (5)	0.7223 (3)	0.6932 (3)	0.0433 (9)
C9	−0.1854 (6)	0.6932 (2)	0.6355 (3)	0.0478 (10)
C10	0.2471 (4)	0.77787 (18)	0.8711 (3)	0.0356 (7)
H1A	−0.308 (5)	0.443 (2)	0.762 (3)	0.030 (9)*
H1B	−0.117 (5)	0.443 (2)	0.759 (3)	0.028 (9)*
H2A	−0.353 (4)	0.549 (2)	0.629 (3)	0.023 (8)*
H2B	−0.284 (5)	0.464 (2)	0.587 (3)	0.038 (10)*
H3A	−0.127 (5)	0.562 (2)	0.530 (3)	0.033 (9)*
H3B	−0.005 (4)	0.514 (2)	0.624 (3)	0.024 (8)*
H4A	0.413 (4)	0.562 (2)	1.076 (3)	0.027 (8)*
H4B	0.353 (4)	0.526 (2)	0.960 (3)	0.022 (8)*
H5A	0.477 (4)	0.688 (2)	1.004 (2)	0.017 (7)*
H5B	0.589 (5)	0.617 (2)	0.974 (3)	0.027 (9)*
H6A	0.498 (4)	0.6915 (19)	0.822 (2)	0.020 (7)*
H6B	0.403 (4)	0.6070 (19)	0.800 (2)	0.017 (7)*
H7A	0.1858	0.6086	0.6278	0.052*
H7B	0.0711	0.6762	0.5497	0.052*
H8A	0.1359	0.7739	0.6806	0.052*
H8B	0.3143	0.7325	0.6740	0.052*
H9A	−0.1460	0.7449	0.6735	0.072*
H9B	−0.2876	0.6732	0.6562	0.072*
H9C	−0.2146	0.7028	0.5573	0.072*
H10A	0.2703	0.7655	0.9485	0.053*
H10B	0.1364	0.8067	0.8472	0.053*
H10C	0.3393	0.8130	0.8584	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01653 (17)	0.01475 (17)	0.01300 (16)	0.00004 (11)	0.00584 (12)	0.00248 (11)
Ni2	0.0134 (2)	0.0146 (2)	0.0115 (2)	−0.00204 (16)	0.00396 (15)	0.00100 (15)
Cl1	0.0182 (3)	0.0289 (3)	0.0237 (3)	0.0002 (2)	−0.0003 (2)	−0.0014 (3)
S1	0.0151 (3)	0.0209 (3)	0.0145 (3)	0.0007 (2)	0.0053 (2)	0.0034 (2)
S2	0.0182 (3)	0.0161 (3)	0.0133 (3)	−0.0033 (2)	0.0064 (2)	−0.0009 (2)
O1	0.0498 (17)	0.120 (3)	0.0414 (15)	0.0461 (19)	0.0037 (13)	−0.0256 (17)
O2	0.0267 (11)	0.0350 (12)	0.0436 (13)	0.0125 (9)	0.0061 (9)	−0.0016 (10)
O3	0.0362 (13)	0.0549 (15)	0.0302 (12)	−0.0205 (12)	−0.0056 (10)	0.0011 (11)
O4	0.0394 (15)	0.0534 (17)	0.098 (2)	−0.0159 (13)	−0.0057 (15)	0.0363 (17)
N1	0.0326 (13)	0.0209 (11)	0.0140 (10)	−0.0057 (9)	0.0066 (9)	0.0031 (8)
N2	0.0195 (11)	0.0279 (12)	0.0220 (11)	0.0008 (9)	0.0071 (9)	0.0125 (9)
C1	0.0269 (15)	0.0270 (14)	0.0168 (12)	−0.0116 (12)	0.0028 (10)	0.0000 (11)
C2	0.0315 (16)	0.0348 (16)	0.0161 (12)	−0.0104 (13)	0.0001 (11)	0.0015 (12)
C3	0.0282 (14)	0.0242 (14)	0.0146 (11)	0.0002 (11)	0.0065 (10)	0.0005 (10)
C4	0.0160 (12)	0.0272 (14)	0.0194 (12)	−0.0016 (10)	0.0028 (10)	0.0074 (11)
C5	0.0178 (13)	0.0273 (14)	0.0221 (13)	−0.0043 (11)	0.0045 (10)	0.0030 (11)
C6	0.0194 (13)	0.0225 (13)	0.0210 (12)	−0.0005 (10)	0.0095 (10)	0.0016 (10)
C7	0.052 (2)	0.055 (2)	0.0265 (15)	−0.0176 (18)	0.0173 (15)	0.0042 (15)
C8	0.0329 (17)	0.068 (2)	0.0264 (15)	−0.0106 (17)	0.0029 (13)	0.0233 (16)
C9	0.076 (3)	0.0329 (18)	0.0271 (16)	0.0233 (18)	−0.0007 (16)	0.0034 (14)
C10	0.0289 (16)	0.0184 (14)	0.064 (2)	−0.0007 (12)	0.0207 (15)	0.0058 (14)

Geometric parameters (Å, º) top

Ni1—N1	1.969 (2)	C4—H4B	0.98 (3)
Ni1—N2	1.993 (2)	C5—C6	1.513 (4)
Ni1—S1	2.1709 (8)	C5—H5A	0.95 (3)
Ni1—S2	2.1777 (8)	C5—H5B	0.97 (4)
Ni2—S1	2.1938 (7)	C6—N2	1.498 (3)
Ni2—S2	2.1921 (7)	C6—H6A	0.98 (3)
Cl1—O1	1.432 (3)	C6—H6B	0.98 (3)
Cl1—O2	1.430 (2)	C7—C8	1.454 (5)
Cl1—O3	1.425 (2)	C7—N1	1.529 (4)
Cl1—O4	1.426 (3)	C7—H7A	0.9900
C1—C2	1.518 (4)	C7—H7B	0.9900
C1—S1	1.824 (3)	C8—N2	1.481 (4)
C1—H1A	0.97 (4)	C8—H8A	0.9900
C1—H1B	0.89 (4)	C8—H8B	0.9900
C2—C3	1.520 (4)	C9—N1	1.466 (4)
C2—H2A	1.00 (3)	C9—H9A	0.9800
C2—H2B	0.97 (4)	C9—H9B	0.9800
C3—N1	1.491 (3)	C9—H9C	0.9800
C3—H3A	0.98 (4)	C10—N2	1.510 (4)
C3—H3B	0.99 (3)	C10—H10A	0.9800
C4—C5	1.519 (4)	C10—H10B	0.9800
C4—S2	1.836 (3)	C10—H10C	0.9800
C4—H4A	0.94 (3)	Ni1—Ni2	3.1518 (6)

N1—Ni1—N2	88.90 (9)	C3—C2—H2A	109.8 (19)
N1—Ni1—S1	95.68 (7)	C1—C2—H2B	108 (2)
N2—Ni1—S1	174.27 (7)	C3—C2—H2B	105 (2)
N1—Ni1—S2	176.66 (7)	H2A—C2—H2B	112 (3)
N2—Ni1—S2	93.34 (7)	N1—C3—H3A	108 (2)
S1—Ni1—S2	82.24 (3)	C2—C3—H3A	112 (2)
S1—Ni2—S2	81.39 (3)	N1—C3—H3B	107.9 (19)
S1—Ni2—S2ⁱ	98.61 (3)	C2—C3—H3B	108.7 (19)
Ni1—S1—C1	105.91 (10)	H3A—C3—H3B	104 (3)
Ni2—S1—C1	106.63 (10)	C5—C4—H4A	112 (2)
Ni1—S2—C4	100.09 (9)	S2—C4—H4A	106 (2)
Ni2—S2—C4	102.93 (9)	C5—C4—H4B	110.2 (19)
Ni1—S1—Ni2	92.46 (3)	S2—C4—H4B	107.8 (19)
Ni1—S2—Ni2	92.32 (2)	H4A—C4—H4B	109 (3)
O3—Cl1—O4	109.37 (17)	C6—C5—H5A	110.1 (18)
O3—Cl1—O2	111.38 (16)	C4—C5—H5A	108.8 (18)
O4—Cl1—O2	110.42 (16)	C6—C5—H5B	105 (2)
O3—Cl1—O1	107.56 (19)	C4—C5—H5B	109 (2)
O4—Cl1—O1	109.6 (2)	H5A—C5—H5B	110 (3)
O2—Cl1—O1	108.46 (16)	N2—C6—H6A	108.8 (18)
C2—C1—S1	111.9 (2)	C5—C6—H6A	109.7 (18)
C1—C2—C3	113.9 (2)	N2—C6—H6B	106.0 (18)
N1—C3—C2	115.7 (2)	C5—C6—H6B	111.5 (18)
C5—C4—S2	112.6 (2)	H6A—C6—H6B	105 (2)
C6—C5—C4	114.5 (2)	C8—C7—H7A	109.5
N2—C6—C5	115.0 (2)	N1—C7—H7A	109.5
C8—C7—N1	110.6 (3)	C8—C7—H7B	109.5
C7—C8—N2	109.8 (3)	N1—C7—H7B	109.5
C9—N1—C3	110.5 (2)	H7A—C7—H7B	108.1
C9—N1—C7	111.3 (3)	C7—C8—H8A	109.7
C3—N1—C7	104.3 (2)	N2—C8—H8A	109.7
C9—N1—Ni1	110.34 (19)	C7—C8—H8B	109.7
C3—N1—Ni1	117.14 (16)	N2—C8—H8B	109.7
C7—N1—Ni1	102.81 (18)	H8A—C8—H8B	108.2
C8—N2—C6	109.9 (2)	N1—C9—H9A	109.5
C8—N2—C10	106.2 (3)	N1—C9—H9B	109.5
C6—N2—C10	108.4 (2)	H9A—C9—H9B	109.5
C8—N2—Ni1	106.90 (19)	N1—C9—H9C	109.5
C6—N2—Ni1	113.38 (16)	H9A—C9—H9C	109.5
C10—N2—Ni1	111.83 (17)	H9B—C9—H9C	109.5
C2—C1—H1A	110 (2)	N2—C10—H10A	109.5
S1—C1—H1A	106 (2)	N2—C10—H10B	109.5
C2—C1—H1B	108 (2)	H10A—C10—H10B	109.5
S1—C1—H1B	109 (2)	N2—C10—H10C	109.5
H1A—C1—H1B	112 (3)	H10A—C10—H10C	109.5
C1—C2—H2A	108.7 (18)	H10B—C10—H10C	109.5

S1—C1—C2—C3	67.6 (3)	S1—Ni1—Ni2—S2ⁱ	37.83 (4)
C1—C2—C3—N1	−69.6 (3)	S2—Ni1—Ni2—S2ⁱ	180.0
S2—C4—C5—C6	−67.3 (3)	N1—Ni1—Ni2—S2	177.99 (10)
C4—C5—C6—N2	65.5 (3)	N2—Ni1—Ni2—S2	30.68 (10)
N1—C7—C8—N2	51.0 (4)	S1—Ni1—Ni2—S2	−142.17 (4)
C2—C3—N1—C9	−63.8 (3)	N1—Ni1—Ni2—S1ⁱ	140.16 (10)
C2—C3—N1—C7	176.5 (3)	N2—Ni1—Ni2—S1ⁱ	−7.16 (10)
C2—C3—N1—Ni1	63.7 (3)	S1—Ni1—Ni2—S1ⁱ	180.0
C8—C7—N1—C9	74.6 (4)	S2—Ni1—Ni2—S1ⁱ	−37.83 (4)
C8—C7—N1—C3	−166.2 (3)	N1—Ni1—Ni2—S1	−39.84 (10)
C8—C7—N1—Ni1	−43.5 (3)	N2—Ni1—Ni2—S1	172.84 (10)
C7—C8—N2—C6	92.5 (3)	S2—Ni1—Ni2—S1	142.17 (4)
C7—C8—N2—C10	−150.5 (3)	C2—C1—S1—Ni1	−57.8 (2)
C7—C8—N2—Ni1	−31.0 (4)	C2—C1—S1—Ni2	−155.3 (2)
C5—C6—N2—C8	173.2 (3)	N1—Ni1—S1—C1	43.83 (13)
C5—C6—N2—C10	57.6 (3)	S2—Ni1—S1—C1	−133.54 (11)
C5—C6—N2—Ni1	−67.2 (3)	Ni2—Ni1—S1—C1	−108.06 (11)
C9—N1—Ni1—N2	−98.6 (2)	N1—Ni1—S1—Ni2	151.89 (7)
C3—N1—Ni1—N2	133.8 (2)	S2—Ni1—S1—Ni2	−25.48 (2)
C7—N1—Ni1—N2	20.1 (2)	S2ⁱ—Ni2—S1—C1	−47.23 (10)
C9—N1—Ni1—S1	77.9 (2)	S2—Ni2—S1—C1	132.77 (10)
C3—N1—Ni1—S1	−49.7 (2)	Ni1—Ni2—S1—C1	107.41 (10)
C7—N1—Ni1—S1	−163.34 (19)	S2ⁱ—Ni2—S1—Ni1	−154.64 (2)
C9—N1—Ni1—Ni2	104.5 (2)	S2—Ni2—S1—Ni1	25.36 (2)
C3—N1—Ni1—Ni2	−23.1 (2)	C5—C4—S2—Ni1	64.9 (2)
C7—N1—Ni1—Ni2	−136.74 (18)	C5—C4—S2—Ni2	159.63 (18)
C8—N2—Ni1—N1	4.8 (2)	N2—Ni1—S2—C4	−54.60 (12)
C6—N2—Ni1—N1	−116.41 (18)	S1—Ni1—S2—C4	129.07 (10)
C10—N2—Ni1—N1	120.7 (2)	Ni2—Ni1—S2—C4	103.57 (10)
C8—N2—Ni1—S2	−177.6 (2)	N2—Ni1—S2—Ni2	−158.17 (7)
C6—N2—Ni1—S2	61.11 (17)	S1—Ni1—S2—Ni2	25.50 (2)
C10—N2—Ni1—S2	−61.82 (19)	S1ⁱ—Ni2—S2—C4	53.82 (9)
C8—N2—Ni1—Ni2	161.56 (19)	S1—Ni2—S2—C4	−126.18 (9)
C6—N2—Ni1—Ni2	40.3 (2)	Ni1—Ni2—S2—C4	−100.91 (9)
C10—N2—Ni1—Ni2	−82.6 (2)	S1ⁱ—Ni2—S2—Ni1	154.73 (2)
N1—Ni1—Ni2—S2ⁱ	−2.01 (10)	S1—Ni2—S2—Ni1	−25.27 (2)
N2—Ni1—Ni2—S2ⁱ	−149.32 (10)

Symmetry code: (i) −x, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	[Ni₃(C₁₀H₂₂N₂S₂)₂](ClO₄)₂
M_r	843.83
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	123
a, b, c (Å)	8.0253 (19), 16.208 (4), 12.807 (3)
β (°)	105.033 (6)
V (Å³)	1608.8 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.21
Crystal size (mm)	0.24 × 0.24 × 0.17

Data collection
Diffractometer	Rigaku AFC7 (Mercury CCD) diffractometer
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.619, 0.705
No. of measured, independent and observed [F² > 2.0σ(F²)] reflections	15030, 3626, 3391
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.082, 1.04
No. of reflections	3626
No. of parameters	235
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.71, −0.70

Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and publCIF (Westrip, 2010).

References

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