Bis(diethyl­enetriamine-κ3N,N′,N′′)nickel(II) bis­(1,2-dicyanoethene-1,2-dithiolato-κ2S,S′)nickel(II)

Zhang, D.-P.; Wang, H.-L.; Zhang, L.-F.; Ni, Z.-H.

doi:10.1107/S1600536808028663

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Pages m1264-m1265

doi:10.1107/S1600536808028663

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Bis(diethylenetriamine-κ³N,N′,N′′)nickel(II) bis(1,2-dicyanoethene-1,2-dithiolato-κ²S,S′)nickel(II)

Dao-Peng Zhang,^a Hai-Long Wang,^a Li-Fang Zhang ^a ^* and Zhong-Hai Ni ^a

^aSchool of Chemistry & Chemical Technology, Shandong University, Jinan 250100, People's Republic of China
^*Correspondence e-mail: Zhanglf@sdu.edu.cn

(Received 20 August 2008; accepted 8 September 2008; online 13 September 2008)

The title compound, [Ni(C₄H₁₃N₃)₂][Ni(C₄N₂S₂)₂], has been synthesized by the reaction of Ni(ClO₄)₂·6H₂O, diethylenetriamine (deta) and Na₂[Ni(mnt)₂] [mnt = maleonitriledithiolate(2-)] in methanol. The structure is composed of a [Ni(deta)₂]²⁺ cation and a [Ni(mnt)₂]²⁻ anion. The coordination geometry of the Ni^II ion in the cation is slightly distorted octahedral, defined by six N atoms from two deta ligands, while the Ni^II ion in the anion is four-coordinated by four S atoms from two mnt ligands in a slightly distorted square-planar geometry. The cations and anions are connected by N—H⋯N hydrogen bonds.

Related literature

For related literature, see: Bois et al. (1998 ); Keum et al. (1992 ); Miller et al. (1989 ); Ren et al. (2001 ); Robertson & Cronin (2002 ); Simmons et al. (1962 ).

Experimental

Crystal data

[Ni(C₄H₁₃N₃)₂][Ni(C₄N₂S₂)₂]
M_r = 604.13
Monoclinic, P 2₁ /n
a = 9.589 (3) Å
b = 16.910 (5) Å
c = 16.146 (4) Å
β = 97.491 (4)°
V = 2595.8 (13) Å³
Z = 4
Mo Kα radiation
μ = 1.80 mm⁻¹
T = 273 (2) K
0.19 × 0.17 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.717, T_max = 0.766
13610 measured reflections
5065 independent reflections
3393 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.109
S = 0.99
5065 reflections
329 parameters
10 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Ni1—S1	2.1739 (12)
Ni1—S2	2.1617 (12)
Ni1—S3	2.1732 (12)
Ni1—S4	2.1658 (12)
Ni2—N5	2.164 (3)
Ni2—N6	2.065 (3)
Ni2—N7	2.150 (4)
Ni2—N8	2.145 (3)
Ni2—N9	2.071 (4)
Ni2—N10	2.151 (3)

S2—Ni1—S4	87.98 (5)
S2—Ni1—S3	168.77 (5)
S4—Ni1—S3	92.72 (4)
S2—Ni1—S1	92.58 (4)
S4—Ni1—S1	170.10 (4)
S3—Ni1—S1	88.65 (4)
N6—Ni2—N9	177.56 (15)
N6—Ni2—N8	98.00 (14)
N9—Ni2—N8	81.73 (14)
N6—Ni2—N7	82.24 (16)
N9—Ni2—N7	95.37 (17)
N8—Ni2—N7	95.96 (15)
N6—Ni2—N10	98.69 (14)
N9—Ni2—N10	81.72 (14)
N8—Ni2—N10	163.04 (16)
N7—Ni2—N10	89.25 (16)
N6—Ni2—N5	81.47 (14)
N9—Ni2—N5	100.96 (15)
N8—Ni2—N5	91.32 (13)
N7—Ni2—N5	162.93 (16)
N10—Ni2—N5	88.20 (14)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯N4ⁱ	0.86 (3)	2.30 (4)	3.098 (6)	154 (3)
N5—H5B⋯N2ⁱⁱ	0.86 (3)	2.48 (3)	3.186 (5)	140 (4)
N7—H7A⋯N3ⁱⁱⁱ	0.86 (4)	2.56 (3)	3.207 (7)	134 (3)
N8—H8B⋯N3ⁱⁱⁱ	0.86 (3)	2.48 (4)	3.164 (6)	138 (3)
N9—H9A⋯N1^iv	0.86 (2)	2.58 (3)	3.387 (6)	156 (5)
N10—H10C⋯N2ⁱⁱ	0.87 (3)	2.34 (3)	3.198 (5)	173 (5)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) x+1, y, z; (iv) $[-x+{\script{5\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808028663/hy2151sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808028663/hy2151Isup2.hkl

checkCIF report

Comment top

Bidentate dithiolate ligands form well square-planar complexes with nickel ions in different oxidation states. Due to their unique properties and potential applications in such areas as conducting and magnetic materials, nearinfrared dyes, nonlinear optical materials (Robertson & Cronin, 2002), the ion-pair complexes formed from [M(mnt)₂]^n- (M = Ni, Pd, Pt or Cu) and transition metal complex cations have been intensively studied (Bois et al., 1998; Miller et al., 1989; Ren et al., 2001). We report here a new ion-pair complex.

The title compound is composed of a [Ni(deta)₂]²⁺ cation and a [Ni(mnt)₂]^2- anion [deta = diethylenetriamine; mnt = maleonitriledithiolate(2-)] (Fig. 1). In the cation, the Ni^II ion has a slightly distorted octahedral geometry, formed by six N atoms from two deta ligands, with the Ni—N distances in a range from 2.065 (3) to 2.164 (3) Å (Table 1), which are consistent with the corresponding values in [Ni(en)₃][Ni(mnt)₂] (en = ethylenediamine) (Keum et al., 1992). The Ni^II ion in the anion is four-coordinated by four S atoms and these five atoms form a square plane with a mean deviation of 0.161 (6) Å. The Ni—S bond lengths [2.1617 (12)–2.1739 (12) Å] are also in agreement with those found in the above complex. The cations and anions are connected by N—H···N hydrogen bonds (Table 2).

Related literature top

For related literature, see: Bois et al. (1998); Keum et al. (1992); Miller et al. (1989); Ren et al. (2001); Robertson & Cronin (2002); Simmons et al. (1962).

Experimental top

The synthesis procedure of the title compound was as following: Ni(ClO₄)₂.6H₂O (0.037 g, 0.10 mmol) was dissolved in methanol (10 ml) at room temperature with stirring and then deta (0.021 g, 0.20 mmol) was added. A solution of Na₂[Ni(mnt)₂] (0.033 g, 0.10 mmol) (Simmons et al., 1962) in methanol (10 ml) was slowly added to the above solution and the mixture was stirred for another 30 min. After filtering, the filtrate was undisturbed for about two weeks at room temperature in air to produce blue crystals suitable for X-ray diffraction (yield 61.75%, 0.037 g). Analysis, calculated for C₁₆H₂₆N₁₀Ni₂S₄: C 31.81, H 4.34, N 23.19%; found: C 31.76, H 4.31, N 23.24%.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.

Bis(diethylenetriamine-κ³N,N',N'')nickel(II) bis(1,2-dicyanoethene-1,2-dithiolato-κ²S,S')nickel(II) top

Crystal data top

[Ni(C₄H₁₃N₃)₂][Ni(C₄N₂S₂)₂]	F(000) = 1248
M_r = 604.13	D_x = 1.546 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3163 reflections
a = 9.589 (3) Å	θ = 2.4–23.8°
b = 16.910 (5) Å	µ = 1.80 mm⁻¹
c = 16.146 (4) Å	T = 273 K
β = 97.491 (4)°	Block, blue
V = 2595.8 (13) Å³	0.19 × 0.17 × 0.15 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	5065 independent reflections
Radiation source: fine-focus sealed tube	3393 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.717, T_max = 0.766	k = −20→19
13610 measured reflections	l = −17→19

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ²(F_o²) + (0.058P)²] where P = (F_o² + 2F_c²)/3
5065 reflections	(Δ/σ)_max < 0.001
329 parameters	Δρ_max = 0.86 e Å⁻³
10 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

[Ni(C₄H₁₃N₃)₂][Ni(C₄N₂S₂)₂]	V = 2595.8 (13) Å³
M_r = 604.13	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.589 (3) Å	µ = 1.80 mm⁻¹
b = 16.910 (5) Å	T = 273 K
c = 16.146 (4) Å	0.19 × 0.17 × 0.15 mm
β = 97.491 (4)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	5065 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3393 reflections with I > 2σ(I)
T_min = 0.717, T_max = 0.766	R_int = 0.037
13610 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	10 restraints
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.86 e Å⁻³
5065 reflections	Δρ_min = −0.26 e Å⁻³
329 parameters

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

	x	y	z	U_iso*/U_eq
Ni1	0.72467 (5)	0.23459 (3)	0.01993 (3)	0.04722 (16)
Ni2	0.97276 (5)	0.40148 (3)	0.25321 (3)	0.04194 (15)
S1	0.78132 (10)	0.13475 (6)	0.10229 (6)	0.0555 (3)
S2	0.90403 (11)	0.21706 (7)	−0.04639 (7)	0.0638 (3)
S3	0.52234 (11)	0.23887 (7)	0.06673 (7)	0.0598 (3)
S4	0.68871 (10)	0.34610 (6)	−0.04535 (7)	0.0576 (3)
N1	1.0808 (4)	0.0021 (3)	0.1686 (3)	0.0828 (12)
N2	1.2281 (4)	0.0992 (2)	−0.0397 (2)	0.0727 (11)
N3	0.1991 (4)	0.3603 (3)	0.0519 (3)	0.0980 (15)
N4	0.3914 (5)	0.4842 (3)	−0.1113 (3)	0.0902 (13)
N5	0.7588 (4)	0.4323 (2)	0.2690 (2)	0.0532 (8)
N6	0.8844 (4)	0.2901 (2)	0.2388 (2)	0.0573 (9)
N7	1.1630 (4)	0.3364 (3)	0.2450 (3)	0.0670 (10)
N8	0.9396 (4)	0.4370 (2)	0.1246 (2)	0.0551 (9)
N9	1.0692 (4)	0.5111 (2)	0.2663 (2)	0.0576 (9)
N10	1.0222 (4)	0.4021 (3)	0.3870 (2)	0.0552 (9)
C1	0.9425 (4)	0.1059 (2)	0.0742 (2)	0.0487 (9)
C2	0.9942 (4)	0.1410 (2)	0.0098 (2)	0.0498 (9)
C3	0.4468 (4)	0.3230 (2)	0.0193 (2)	0.0546 (10)
C4	0.5168 (4)	0.3686 (2)	−0.0311 (2)	0.0532 (10)
C5	1.0189 (4)	0.0466 (3)	0.1249 (3)	0.0587 (11)
C6	1.1252 (4)	0.1169 (3)	−0.0162 (2)	0.0564 (11)
C7	0.3083 (5)	0.3441 (3)	0.0363 (3)	0.0676 (12)
C8	0.4494 (5)	0.4331 (3)	−0.0751 (3)	0.0656 (12)
C9	0.6713 (4)	0.3606 (3)	0.2543 (3)	0.0690 (12)
H9C	0.6357	0.3564	0.1954	0.083*
H9B	0.5916	0.3639	0.2854	0.083*
C10	0.7577 (5)	0.2887 (3)	0.2815 (3)	0.0711 (13)
H10A	0.7841	0.2894	0.3416	0.085*
H10B	0.7039	0.2410	0.2668	0.085*
C11	0.9946 (5)	0.2337 (3)	0.2698 (3)	0.0759 (14)
H11A	0.9634	0.1802	0.2563	0.091*
H11B	1.0161	0.2381	0.3301	0.091*
C12	1.1225 (6)	0.2523 (3)	0.2293 (3)	0.0850 (16)
H12A	1.1994	0.2181	0.2518	0.102*
H12B	1.1030	0.2429	0.1696	0.102*
C13	1.0004 (5)	0.5157 (3)	0.1168 (3)	0.0748 (13)
H13A	0.9436	0.5450	0.0730	0.090*
H13B	1.0944	0.5106	0.1013	0.090*
C14	1.0069 (5)	0.5602 (3)	0.1974 (3)	0.0748 (13)
H14A	1.0627	0.6078	0.1945	0.090*
H14B	0.9129	0.5758	0.2066	0.090*
C15	1.0661 (5)	0.5377 (3)	0.3519 (3)	0.0694 (12)
H15A	0.9721	0.5556	0.3585	0.083*
H15B	1.1303	0.5818	0.3639	0.083*
C16	1.1076 (5)	0.4719 (3)	0.4112 (2)	0.0704 (13)
H16A	1.2063	0.4595	0.4109	0.084*
H16B	1.0943	0.4879	0.4674	0.084*
H8A	0.8544 (16)	0.441 (2)	0.101 (2)	0.051 (11)*
H8B	0.971 (4)	0.4005 (18)	0.095 (2)	0.073 (15)*
H7A	1.219 (4)	0.352 (3)	0.211 (2)	0.090 (17)*
H10C	0.944 (3)	0.406 (3)	0.408 (3)	0.091 (17)*
H5A	0.727 (5)	0.4692 (19)	0.235 (2)	0.093 (18)*
H6A	0.860 (4)	0.281 (2)	0.1865 (8)	0.055 (12)*
H7B	1.217 (4)	0.341 (3)	0.2916 (17)	0.12 (2)*
H10D	1.066 (6)	0.362 (3)	0.409 (4)	0.16 (3)*
H9A	1.1581 (18)	0.503 (4)	0.267 (4)	0.16 (3)*
H5B	0.769 (5)	0.448 (3)	0.3200 (12)	0.101 (18)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0377 (3)	0.0536 (3)	0.0497 (3)	0.0057 (2)	0.0033 (2)	−0.0112 (2)
Ni2	0.0429 (3)	0.0502 (3)	0.0324 (2)	−0.0003 (2)	0.00373 (19)	−0.0015 (2)
S1	0.0412 (5)	0.0638 (7)	0.0642 (6)	0.0081 (5)	0.0164 (5)	−0.0001 (5)
S2	0.0514 (6)	0.0822 (8)	0.0599 (6)	0.0189 (6)	0.0160 (5)	0.0104 (6)
S3	0.0503 (6)	0.0652 (7)	0.0663 (7)	0.0126 (5)	0.0161 (5)	−0.0012 (5)
S4	0.0451 (6)	0.0601 (7)	0.0667 (7)	0.0028 (5)	0.0040 (5)	−0.0026 (5)
N1	0.062 (2)	0.098 (3)	0.093 (3)	0.027 (2)	0.024 (2)	0.027 (2)
N2	0.055 (2)	0.110 (3)	0.055 (2)	0.029 (2)	0.0172 (18)	0.016 (2)
N3	0.078 (3)	0.134 (4)	0.089 (3)	0.048 (3)	0.038 (2)	0.009 (3)
N4	0.097 (3)	0.094 (3)	0.077 (3)	0.032 (3)	0.000 (2)	0.008 (2)
N5	0.048 (2)	0.067 (2)	0.044 (2)	0.0015 (18)	0.0033 (16)	−0.0034 (19)
N6	0.067 (2)	0.056 (2)	0.047 (2)	−0.0026 (18)	−0.0011 (18)	−0.0019 (17)
N7	0.055 (2)	0.087 (3)	0.059 (2)	0.014 (2)	0.008 (2)	−0.003 (2)
N8	0.048 (2)	0.077 (3)	0.0393 (19)	0.014 (2)	0.0049 (16)	0.0003 (18)
N9	0.065 (2)	0.059 (2)	0.051 (2)	−0.0045 (19)	0.0138 (17)	−0.0004 (17)
N10	0.042 (2)	0.087 (3)	0.0367 (17)	−0.009 (2)	0.0043 (15)	−0.0018 (18)
C1	0.037 (2)	0.058 (3)	0.051 (2)	0.0068 (18)	0.0077 (17)	−0.0086 (19)
C2	0.037 (2)	0.064 (3)	0.049 (2)	0.0069 (19)	0.0053 (17)	−0.0067 (19)
C3	0.048 (2)	0.068 (3)	0.047 (2)	0.017 (2)	0.0024 (18)	−0.016 (2)
C4	0.050 (2)	0.058 (3)	0.049 (2)	0.013 (2)	−0.0017 (18)	−0.013 (2)
C5	0.043 (2)	0.073 (3)	0.063 (3)	0.007 (2)	0.020 (2)	0.002 (2)
C6	0.051 (2)	0.076 (3)	0.043 (2)	0.016 (2)	0.0078 (18)	0.006 (2)
C7	0.064 (3)	0.087 (3)	0.053 (3)	0.025 (3)	0.014 (2)	−0.003 (2)
C8	0.063 (3)	0.077 (3)	0.054 (3)	0.018 (2)	−0.003 (2)	−0.005 (2)
C9	0.048 (2)	0.092 (4)	0.067 (3)	−0.018 (3)	0.006 (2)	−0.014 (3)
C10	0.073 (3)	0.070 (3)	0.071 (3)	−0.026 (3)	0.014 (2)	−0.002 (2)
C11	0.093 (4)	0.057 (3)	0.073 (3)	0.009 (3)	−0.009 (3)	0.008 (2)
C12	0.096 (4)	0.072 (4)	0.082 (3)	0.032 (3)	−0.005 (3)	−0.009 (3)
C13	0.090 (3)	0.081 (4)	0.056 (3)	0.004 (3)	0.021 (2)	0.023 (2)
C14	0.087 (4)	0.052 (3)	0.085 (3)	−0.001 (2)	0.012 (3)	0.008 (2)
C15	0.070 (3)	0.067 (3)	0.071 (3)	−0.005 (2)	0.010 (2)	−0.028 (2)
C16	0.066 (3)	0.100 (4)	0.045 (2)	−0.025 (3)	0.006 (2)	−0.013 (2)

Geometric parameters (Å, º) top

Ni1—S1	2.1739 (12)	N9—C15	1.456 (5)
Ni1—S2	2.1617 (12)	N9—H9A	0.86 (3)
Ni1—S3	2.1732 (12)	N10—C16	1.461 (5)
Ni1—S4	2.1658 (12)	N10—H10C	0.87 (3)
Ni2—N5	2.164 (3)	N10—H10D	0.85 (6)
Ni2—N6	2.065 (3)	C1—C2	1.347 (5)
Ni2—N7	2.150 (4)	C1—C5	1.434 (6)
Ni2—N8	2.145 (3)	C2—C6	1.434 (5)
Ni2—N9	2.071 (4)	C3—C4	1.359 (6)
Ni2—N10	2.151 (3)	C3—C7	1.436 (5)
S1—C1	1.737 (4)	C4—C8	1.412 (6)
S2—C2	1.738 (4)	C9—C10	1.505 (6)
S3—C3	1.730 (4)	C9—H9C	0.9700
S4—C4	1.737 (4)	C9—H9B	0.9700
N1—C5	1.144 (5)	C10—H10A	0.9700
N2—C6	1.143 (5)	C10—H10B	0.9700
N3—C7	1.141 (5)	C11—C12	1.497 (7)
N4—C8	1.146 (5)	C11—H11A	0.9700
N5—C9	1.477 (5)	C11—H11B	0.9700
N5—H5A	0.86 (3)	C12—H12A	0.9700
N5—H5B	0.86 (3)	C12—H12B	0.9700
N6—C11	1.463 (5)	C13—C14	1.497 (6)
N6—C10	1.473 (5)	C13—H13A	0.9700
N6—H6A	0.86 (2)	C13—H13B	0.9700
N7—C12	1.486 (6)	C14—H14A	0.9700
N7—H7A	0.86 (4)	C14—H14B	0.9700
N7—H7B	0.86 (4)	C15—C16	1.488 (6)
N8—C13	1.466 (6)	C15—H15A	0.9700
N8—H8A	0.86 (3)	C15—H15B	0.9700
N8—H8B	0.86 (3)	C16—H16A	0.9700
N9—C14	1.453 (5)	C16—H16B	0.9700

S2—Ni1—S4	87.98 (5)	C5—C1—S1	117.0 (3)
S2—Ni1—S3	168.77 (5)	C1—C2—C6	121.7 (4)
S4—Ni1—S3	92.72 (4)	C1—C2—S2	121.4 (3)
S2—Ni1—S1	92.58 (4)	C6—C2—S2	116.9 (3)
S4—Ni1—S1	170.10 (4)	C4—C3—C7	121.0 (4)
S3—Ni1—S1	88.65 (4)	C4—C3—S3	121.4 (3)
N6—Ni2—N9	177.56 (15)	C7—C3—S3	117.7 (3)
N6—Ni2—N8	98.00 (14)	C3—C4—C8	120.7 (4)
N9—Ni2—N8	81.73 (14)	C3—C4—S4	120.5 (3)
N6—Ni2—N7	82.24 (16)	C8—C4—S4	118.8 (3)
N9—Ni2—N7	95.37 (17)	N1—C5—C1	176.5 (5)
N8—Ni2—N7	95.96 (15)	N2—C6—C2	177.4 (4)
N6—Ni2—N10	98.69 (14)	N3—C7—C3	178.2 (5)
N9—Ni2—N10	81.72 (14)	N4—C8—C4	178.1 (5)
N8—Ni2—N10	163.04 (16)	N5—C9—C10	109.7 (3)
N7—Ni2—N10	89.25 (16)	N5—C9—H9C	109.7
N6—Ni2—N5	81.47 (14)	C10—C9—H9C	109.7
N9—Ni2—N5	100.96 (15)	N5—C9—H9B	109.7
N8—Ni2—N5	91.32 (13)	C10—C9—H9B	109.7
N7—Ni2—N5	162.93 (16)	H9C—C9—H9B	108.2
N10—Ni2—N5	88.20 (14)	N6—C10—C9	107.8 (3)
C1—S1—Ni1	102.61 (14)	N6—C10—H10A	110.1
C2—S2—Ni1	102.53 (13)	C9—C10—H10A	110.1
C3—S3—Ni1	102.40 (15)	N6—C10—H10B	110.1
C4—S4—Ni1	102.68 (15)	C9—C10—H10B	110.1
C9—N5—Ni2	108.1 (3)	H10A—C10—H10B	108.5
C9—N5—H5A	110 (3)	N6—C11—C12	108.0 (4)
Ni2—N5—H5A	111 (3)	N6—C11—H11A	110.1
C9—N5—H5B	114 (3)	C12—C11—H11A	110.1
Ni2—N5—H5B	101 (3)	N6—C11—H11B	110.1
H5A—N5—H5B	112 (5)	C12—C11—H11B	110.1
C11—N6—C10	115.5 (4)	H11A—C11—H11B	108.4
C11—N6—Ni2	106.8 (3)	N7—C12—C11	109.7 (4)
C10—N6—Ni2	108.3 (3)	N7—C12—H12A	109.7
C11—N6—H6A	108 (3)	C11—C12—H12A	109.7
C10—N6—H6A	109 (3)	N7—C12—H12B	109.7
Ni2—N6—H6A	109 (3)	C11—C12—H12B	109.7
C12—N7—Ni2	107.2 (3)	H12A—C12—H12B	108.2
C12—N7—H7A	110 (3)	N8—C13—C14	110.7 (3)
Ni2—N7—H7A	120 (3)	N8—C13—H13A	109.5
C12—N7—H7B	110 (4)	C14—C13—H13A	109.5
Ni2—N7—H7B	109 (4)	N8—C13—H13B	109.5
H7A—N7—H7B	100 (5)	C14—C13—H13B	109.5
C13—N8—Ni2	109.1 (3)	H13A—C13—H13B	108.1
C13—N8—H8A	105 (3)	N9—C14—C13	110.2 (4)
Ni2—N8—H8A	118 (2)	N9—C14—H14A	109.6
C13—N8—H8B	116 (3)	C13—C14—H14A	109.6
Ni2—N8—H8B	108 (3)	N9—C14—H14B	109.6
H8A—N8—H8B	101 (4)	C13—C14—H14B	109.6
C14—N9—C15	119.5 (4)	H14A—C14—H14B	108.1
C14—N9—Ni2	107.4 (3)	N9—C15—C16	110.1 (4)
C15—N9—Ni2	108.0 (3)	N9—C15—H15A	109.6
C14—N9—H9A	114 (4)	C16—C15—H15A	109.6
C15—N9—H9A	100 (4)	N9—C15—H15B	109.6
Ni2—N9—H9A	107 (5)	C16—C15—H15B	109.6
C16—N10—Ni2	108.4 (3)	H15A—C15—H15B	108.2
C16—N10—H10C	108 (3)	N10—C16—C15	109.8 (3)
Ni2—N10—H10C	108 (3)	N10—C16—H16A	109.7
C16—N10—H10D	108 (5)	C15—C16—H16A	109.7
Ni2—N10—H10D	117 (5)	N10—C16—H16B	109.7
H10C—N10—H10D	107 (5)	C15—C16—H16B	109.7
C2—C1—C5	122.5 (3)	H16A—C16—H16B	108.2
C2—C1—S1	120.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···N4ⁱ	0.86 (3)	2.30 (4)	3.098 (6)	154 (3)
N5—H5B···N2ⁱⁱ	0.86 (3)	2.48 (3)	3.186 (5)	140 (4)
N7—H7A···N3ⁱⁱⁱ	0.86 (4)	2.56 (3)	3.207 (7)	134 (3)
N8—H8B···N3ⁱⁱⁱ	0.86 (3)	2.48 (4)	3.164 (6)	138 (3)
N9—H9A···N1^iv	0.86 (2)	2.58 (3)	3.387 (6)	156 (5)
N10—H10C···N2ⁱⁱ	0.87 (3)	2.34 (3)	3.198 (5)	173 (5)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1/2, −y+1/2, z+1/2; (iii) x+1, y, z; (iv) −x+5/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Ni(C₄H₁₃N₃)₂][Ni(C₄N₂S₂)₂]
M_r	604.13
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	273
a, b, c (Å)	9.589 (3), 16.910 (5), 16.146 (4)
β (°)	97.491 (4)
V (Å³)	2595.8 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.80
Crystal size (mm)	0.19 × 0.17 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.717, 0.766
No. of measured, independent and observed [I > 2σ(I)] reflections	13610, 5065, 3393
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.109, 0.99
No. of reflections	5065
No. of parameters	329
No. of restraints	10
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.86, −0.26

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Ni1—S1	2.1739 (12)	Ni2—N6	2.065 (3)
Ni1—S2	2.1617 (12)	Ni2—N7	2.150 (4)
Ni1—S3	2.1732 (12)	Ni2—N8	2.145 (3)
Ni1—S4	2.1658 (12)	Ni2—N9	2.071 (4)
Ni2—N5	2.164 (3)	Ni2—N10	2.151 (3)

S2—Ni1—S4	87.98 (5)	N8—Ni2—N7	95.96 (15)
S2—Ni1—S3	168.77 (5)	N6—Ni2—N10	98.69 (14)
S4—Ni1—S3	92.72 (4)	N9—Ni2—N10	81.72 (14)
S2—Ni1—S1	92.58 (4)	N8—Ni2—N10	163.04 (16)
S4—Ni1—S1	170.10 (4)	N7—Ni2—N10	89.25 (16)
S3—Ni1—S1	88.65 (4)	N6—Ni2—N5	81.47 (14)
N6—Ni2—N9	177.56 (15)	N9—Ni2—N5	100.96 (15)
N6—Ni2—N8	98.00 (14)	N8—Ni2—N5	91.32 (13)
N9—Ni2—N8	81.73 (14)	N7—Ni2—N5	162.93 (16)
N6—Ni2—N7	82.24 (16)	N10—Ni2—N5	88.20 (14)
N9—Ni2—N7	95.37 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···N4ⁱ	0.86 (3)	2.30 (4)	3.098 (6)	154 (3)
N5—H5B···N2ⁱⁱ	0.86 (3)	2.48 (3)	3.186 (5)	140 (4)
N7—H7A···N3ⁱⁱⁱ	0.86 (4)	2.56 (3)	3.207 (7)	134 (3)
N8—H8B···N3ⁱⁱⁱ	0.86 (3)	2.48 (4)	3.164 (6)	138 (3)
N9—H9A···N1^iv	0.86 (2)	2.58 (3)	3.387 (6)	156 (5)
N10—H10C···N2ⁱⁱ	0.87 (3)	2.34 (3)	3.198 (5)	173 (5)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1/2, −y+1/2, z+1/2; (iii) x+1, y, z; (iv) −x+5/2, y+1/2, −z+1/2.

Acknowledgements

This work was supported by the Natural Science Foundation of China (No. 20701027) and the Postdoctoral Scientific Foundation of China (No. 200704211076).

References

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