Bis[1-(eth­oxy­carbonyl­meth­yl)pyridinium] bis­(1,2-dicyano­ethene-1,2-dithiol­ato-κ2S,S′)nickelate(II)

Ren, T.; Yang, C.; Fang, D.; Shi, G.; Zhu, X.

doi:10.1107/S1600536812033831

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page m1151

doi:10.1107/S1600536812033831

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Bis[1-(ethoxycarbonylmethyl)pyridinium] bis(1,2-dicyanoethene-1,2-dithiolato-κ²S,S′)nickelate(II)

Tian-li Ren,^a Cheng-jian Yang,^a ^* De-yu Fang,^a Guo-xun Shi ^a and Xue Zhu ^b

^aDepartment of Immunology and Rheumatology, the Second People's Hospital of Wuxi, Wuxi 214002, People's Republic of China, and ^bKey Laboratory of Nuclear Medicine, Ministry of Health, Jiangsu Key Laboratory of Molecular Nuclear Medicine, Jiangsu Institute of Nuclear Medicine. Wuxi 214063, People's Republic of China
^*Correspondence e-mail: yangcj12@126.com

(Received 9 July 2012; accepted 28 July 2012; online 4 August 2012)

The asymmetric unit of the title ion-pair complex, (C₉H₁₂NO₂)₂[Ni(C₄N₂S₂)₂], contains two 1-(ethoxycarbonylmethyl)pyridinium cations and one bis(1,2-dicyanoethene-1,2-dithiolato)nickelate(II) dianion, which exhibits a slightly distorted square-planar coordination geometry. In the crystal, the cations are linked by strong C—H⋯O hydrogen bonds into C(6) chains along [100]. The cations and anions are linked into a three-dimensional architecture by weak C—H⋯N and C—H⋯S interactions.

Related literature

For details of other maleonitriledithiolate metal complexes, see: Robertson & Cronin (2002 ); Coomber et al. (1996 ); Duan et al. (2010 ); Wang et al. (2012 ). For general background to the use of maleonitriledithiolate transition metal complexes as building blocks for optical, magnetic and conducting molecular materials, see: Brammer (2004 ); Ni et al. (2005 ); Robin & Fromm (2006 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

(C₉H₁₂NO₂)₂[Ni(C₄N₂S₂)₂]
M_r = 671.46
Monoclinic, P 2₁ /c
a = 9.486 (2) Å
b = 19.542 (5) Å
c = 17.635 (4) Å
β = 104.803 (4)°
V = 3160.6 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.92 mm⁻¹
T = 291 K
0.30 × 0.15 × 0.10 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.770, T_max = 0.914
16888 measured reflections
6200 independent reflections
5024 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.114
S = 1.02
6200 reflections
370 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10A⋯O1ⁱ	0.96	2.13	3.064 (4)	164
C13—H13A⋯N6ⁱⁱ	0.96	2.57	3.357 (4)	140
C15—H15B⋯S2	0.96	2.86	3.680 (3)	145
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x+1, y, z.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812033831/bx2420sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812033831/bx2420Isup2.hkl

checkCIF report

Comment top

The maleonitriledithiolate (or 1,2-dicyanoethene-1,2-dithiolate, mnt^2-) transition metal complexes, which is one typical kind of bis-1,2-dithiolene complexes, are often used as building blocks for optical, magnetic and conducting molecular materials (Brammer, 2004; Robin & Fromm, 2006; Duan et al., 2010). It has been found that maleonitriledithiolate (mnt^2-) complexes are charge-transfer salts, and they have various structure and the intra- or inter- molecular contacts which can result in large changes of physical properties of the complexes based on the [M(mnt)₂]^n- (Robertson & Cronin, 2002; Coomber et al., 1996; Ni et al., 2005; Duan et al., 2010; Wang et al., 2012). We report here a new [Ni(mnt)₂]^2- salt containing the 1-(ethoxycarbonylmethyl)pyridinium cation, (EtOAcPy)⁺, as shown in Fig. 1. The asymmetric unit contains two (EtOAcPy)⁺cation and one [Ni(mnt)₂^2-] dianion. The [Ni(mnt)₂]^2- dianion exhibits a slightly distorted square-planar coordination geometry. In the crystal, cations are linked by strong C—H···O hydrogen bond into chains with graph-set notation C(6) along [100] (Bernstein et al., 1995). The cations and anions are linked by weak C—H ··· N and C—H··· S interactions (Table 1).

Related literature top

For details of other maleonitriledithiolate metal complexes, see: Robertson & Cronin (2002); Coomber et al. (1996); Duan et al. (2010); Wang et al. (2012). For general background to the use of maleonitriledithiolate transition metal complexes as building blocks for optical, magnetic and conducting molecular materials, see: Brammer (2004); Ni et al. (2005); Robin & Fromm (2006). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

The title compound was prepared by the direct reaction of NiCl₂.6H₂O, Na₂mnt and (EtOAcPy)⁺.Br^- in the mixed solution of ethanol and H₂O (1:1). Red–brown block-like single crystals were obtained by slow evaporation of the acetonitrile solution at room temperature for about one week.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound with atom labels. Displacement ellipsoids were draw at the 30% probability.
	Fig. 2. The packing diagram of title complex as viewed along a axis. (dotted lines are H-bonds between cations and anions)

Bis[1-(ethoxycarbonylmethyl)pyridinium] bis(1,2-dicyanoethene-1,2-dithiolato-κ²S,S')nickelate(II) top

Crystal data top

(C₉H₁₂NO₂)₂[Ni(C₄N₂S₂)₂]	F(000) = 1384
M_r = 671.46	D_x = 1.411 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1842 reflections
a = 9.486 (2) Å	θ = 2.4–20.0°
b = 19.542 (5) Å	µ = 0.92 mm⁻¹
c = 17.635 (4) Å	T = 291 K
β = 104.803 (4)°	Block, red-brown
V = 3160.6 (13) Å³	0.30 × 0.15 × 0.10 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	6200 independent reflections
Radiation source: sealed tube	5024 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
phi and ω scans	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
T_min = 0.770, T_max = 0.914	k = −24→24
16888 measured reflections	l = −21→12

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.06P)² + 1.22P] where P = (F_o² + 2F_c²)/3
6200 reflections	(Δ/σ)_max < 0.001
370 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

(C₉H₁₂NO₂)₂[Ni(C₄N₂S₂)₂]	V = 3160.6 (13) Å³
M_r = 671.46	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.486 (2) Å	µ = 0.92 mm⁻¹
b = 19.542 (5) Å	T = 291 K
c = 17.635 (4) Å	0.30 × 0.15 × 0.10 mm
β = 104.803 (4)°

Data collection top

Bruker SMART APEX CCD diffractometer	6200 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	5024 reflections with I > 2σ(I)
T_min = 0.770, T_max = 0.914	R_int = 0.026
16888 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.02	Δρ_max = 0.18 e Å⁻³
6200 reflections	Δρ_min = −0.34 e Å⁻³
370 parameters

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
C1	0.0092 (3)	0.27127 (15)	0.68082 (18)	0.0574 (7)
H1A	−0.0512	0.2503	0.7105	0.069*
C2	−0.0336 (3)	0.27156 (17)	0.60181 (19)	0.0627 (8)
H2A	−0.1235	0.2499	0.5752	0.075*
C3	0.0489 (3)	0.30165 (17)	0.5601 (2)	0.0659 (8)
H3A	0.0172	0.3019	0.5038	0.079*
C4	0.1749 (4)	0.33078 (17)	0.5965 (2)	0.0702 (9)
H4A	0.2352	0.3526	0.5674	0.084*
C5	0.2169 (4)	0.33164 (17)	0.67691 (19)	0.0690 (9)
H5A	0.3086	0.3513	0.7042	0.083*
C6	0.1778 (4)	0.29897 (17)	0.80314 (17)	0.0625 (8)
H6A	0.2808	0.3076	0.8195	0.075*
H6B	0.1605	0.2538	0.8202	0.075*
C7	0.1028 (4)	0.35080 (17)	0.8425 (2)	0.0656 (8)
C8	0.0589 (4)	0.37959 (17)	0.9706 (2)	0.0664 (9)
H8A	0.0711	0.3532	1.0178	0.080*
H8B	−0.0422	0.3875	0.9456	0.080*
C9	0.1514 (4)	0.44077 (17)	0.99563 (19)	0.0657 (8)
H9A	0.1085	0.4676	1.0295	0.099*
H9B	0.2469	0.4261	1.0239	0.099*
H9C	0.1585	0.4679	0.9514	0.099*
C10	0.2726 (4)	0.56883 (17)	0.31523 (19)	0.0632 (8)
H10A	0.1770	0.5767	0.2817	0.076*
C11	0.3033 (4)	0.58304 (16)	0.3941 (2)	0.0678 (9)
H11A	0.2314	0.6030	0.4171	0.081*
C12	0.4402 (4)	0.56894 (17)	0.4396 (2)	0.0664 (8)
H12A	0.4628	0.5784	0.4948	0.080*
C13	0.5375 (3)	0.54072 (16)	0.40850 (19)	0.0608 (7)
H13A	0.6330	0.5314	0.4413	0.073*
C14	0.5035 (3)	0.52757 (16)	0.33203 (18)	0.0605 (7)
H14A	0.5737	0.5057	0.3094	0.073*
C15	0.3445 (4)	0.53147 (17)	0.20264 (18)	0.0658 (8)
H15A	0.2409	0.5290	0.1813	0.079*
H15B	0.3862	0.4883	0.1940	0.079*
C16	0.4074 (3)	0.58706 (15)	0.16235 (18)	0.0580 (7)
C17	0.4174 (4)	0.62653 (17)	0.0371 (2)	0.0668 (9)
H17A	0.5182	0.6357	0.0617	0.080*
H17B	0.3640	0.6688	0.0297	0.080*
C18	0.4040 (4)	0.59306 (18)	−0.03955 (19)	0.0701 (9)
H18A	0.4414	0.6207	−0.0750	0.105*
H18B	0.4569	0.5507	−0.0301	0.105*
H18C	0.3025	0.5838	−0.0622	0.105*
C19	0.5736 (3)	0.30442 (17)	0.31581 (18)	0.0586 (7)
C20	0.7122 (3)	0.27502 (17)	0.34896 (18)	0.0584 (7)
C21	0.5209 (3)	0.30770 (16)	0.23727 (18)	0.0600 (7)
C22	0.6003 (3)	0.27884 (16)	0.18676 (19)	0.0604 (7)
C23	−0.0312 (3)	0.43365 (16)	0.27582 (17)	0.0548 (7)
C24	−0.1682 (3)	0.46578 (17)	0.24053 (18)	0.0613 (7)
C25	0.0161 (3)	0.42632 (17)	0.35483 (17)	0.0570 (7)
C26	−0.0736 (3)	0.44181 (17)	0.40549 (19)	0.0614 (8)
N1	0.1339 (3)	0.30149 (13)	0.71817 (14)	0.0553 (6)
N2	0.3757 (3)	0.54281 (13)	0.28536 (14)	0.0578 (6)
N3	0.8255 (3)	0.25235 (14)	0.37599 (17)	0.0700 (8)
N4	0.6599 (3)	0.25557 (15)	0.14504 (16)	0.0668 (7)
N5	−0.2783 (3)	0.49033 (15)	0.21326 (16)	0.0651 (7)
N6	−0.1470 (3)	0.45396 (14)	0.44550 (16)	0.0645 (7)
Ni1	0.27080 (4)	0.370117 (18)	0.29545 (2)	0.05072 (12)
O1	0.0043 (3)	0.38524 (11)	0.80562 (13)	0.0695 (6)
O2	0.1514 (2)	0.34855 (11)	0.91666 (13)	0.0687 (6)
O3	0.4846 (2)	0.63080 (11)	0.19261 (12)	0.0618 (5)
O4	0.3596 (2)	0.57755 (11)	0.08488 (12)	0.0634 (5)
S1	0.46957 (8)	0.33440 (4)	0.37583 (4)	0.05255 (18)
S2	0.35111 (8)	0.34322 (4)	0.19505 (4)	0.05189 (17)
S3	0.07449 (8)	0.40886 (4)	0.21465 (4)	0.05150 (18)
S4	0.18471 (8)	0.38983 (4)	0.39552 (4)	0.05204 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0555 (17)	0.0526 (16)	0.0653 (18)	−0.0082 (13)	0.0176 (14)	−0.0130 (14)
C2	0.0542 (17)	0.0706 (19)	0.0645 (19)	−0.0201 (15)	0.0173 (14)	−0.0173 (15)
C3	0.0540 (17)	0.076 (2)	0.0641 (19)	−0.0093 (15)	0.0080 (14)	0.0125 (16)
C4	0.076 (2)	0.0659 (19)	0.0649 (19)	−0.0291 (17)	0.0112 (16)	0.0117 (16)
C5	0.069 (2)	0.0648 (19)	0.0645 (19)	−0.0179 (16)	0.0003 (15)	0.0222 (16)
C6	0.0695 (19)	0.0634 (18)	0.0540 (17)	0.0206 (15)	0.0143 (14)	−0.0037 (14)
C7	0.0636 (19)	0.0605 (18)	0.069 (2)	0.0149 (15)	0.0098 (16)	−0.0188 (16)
C8	0.0626 (19)	0.0677 (19)	0.0623 (18)	0.0139 (15)	0.0036 (15)	−0.0193 (15)
C9	0.069 (2)	0.0657 (19)	0.0630 (18)	0.0146 (15)	0.0184 (15)	−0.0181 (15)
C10	0.0568 (18)	0.0680 (19)	0.0641 (19)	0.0133 (15)	0.0142 (14)	0.0103 (15)
C11	0.076 (2)	0.0582 (18)	0.070 (2)	0.0250 (16)	0.0204 (17)	0.0048 (15)
C12	0.067 (2)	0.070 (2)	0.0600 (18)	−0.0121 (16)	0.0110 (15)	−0.0047 (15)
C13	0.0517 (16)	0.0602 (17)	0.068 (2)	−0.0049 (14)	0.0108 (14)	0.0073 (15)
C14	0.0603 (18)	0.0642 (18)	0.0600 (18)	0.0098 (14)	0.0207 (14)	0.0131 (14)
C15	0.077 (2)	0.0613 (18)	0.0574 (17)	−0.0215 (16)	0.0140 (15)	−0.0099 (14)
C16	0.0610 (18)	0.0534 (16)	0.0593 (17)	−0.0091 (14)	0.0150 (14)	−0.0094 (14)
C17	0.068 (2)	0.0584 (18)	0.069 (2)	−0.0180 (15)	0.0078 (16)	0.0077 (15)
C18	0.075 (2)	0.069 (2)	0.0642 (19)	−0.0213 (16)	0.0149 (16)	0.0186 (16)
C19	0.0442 (15)	0.0707 (19)	0.0624 (18)	0.0064 (13)	0.0161 (13)	0.0019 (15)
C20	0.0495 (17)	0.0670 (18)	0.0581 (17)	0.0027 (14)	0.0124 (13)	−0.0007 (14)
C21	0.0587 (17)	0.0632 (18)	0.0604 (18)	0.0127 (14)	0.0197 (14)	0.0052 (14)
C22	0.0602 (18)	0.0597 (17)	0.0644 (18)	0.0173 (14)	0.0216 (15)	0.0124 (14)
C23	0.0404 (14)	0.0676 (18)	0.0581 (17)	0.0016 (12)	0.0156 (12)	0.0073 (14)
C24	0.0545 (18)	0.0698 (19)	0.0603 (18)	0.0118 (15)	0.0162 (14)	0.0024 (15)
C25	0.0513 (16)	0.0680 (18)	0.0525 (16)	0.0062 (13)	0.0147 (13)	−0.0072 (14)
C26	0.0574 (17)	0.0676 (19)	0.0597 (18)	0.0142 (15)	0.0161 (14)	−0.0068 (15)
N1	0.0528 (13)	0.0582 (14)	0.0528 (14)	0.0015 (11)	0.0095 (11)	−0.0033 (11)
N2	0.0492 (14)	0.0653 (15)	0.0577 (14)	−0.0080 (11)	0.0111 (11)	−0.0050 (12)
N3	0.0570 (15)	0.0670 (16)	0.0742 (18)	0.0118 (13)	−0.0050 (13)	−0.0157 (14)
N4	0.0655 (16)	0.0733 (17)	0.0619 (16)	0.0269 (14)	0.0173 (13)	0.0104 (13)
N5	0.0482 (14)	0.0825 (18)	0.0672 (16)	0.0142 (13)	0.0193 (12)	0.0097 (14)
N6	0.0625 (16)	0.0694 (16)	0.0616 (15)	0.0164 (13)	0.0158 (13)	−0.0141 (13)
Ni1	0.0489 (2)	0.0502 (2)	0.0536 (2)	0.00300 (15)	0.01412 (16)	−0.00066 (15)
O1	0.0652 (13)	0.0641 (13)	0.0718 (14)	0.0178 (11)	0.0039 (11)	−0.0198 (11)
O2	0.0707 (14)	0.0654 (13)	0.0651 (14)	0.0163 (11)	0.0085 (11)	−0.0224 (11)
O3	0.0625 (13)	0.0630 (12)	0.0574 (12)	−0.0164 (10)	0.0107 (10)	0.0014 (10)
O4	0.0693 (13)	0.0660 (13)	0.0569 (12)	−0.0244 (11)	0.0195 (10)	−0.0107 (10)
S1	0.0502 (4)	0.0529 (4)	0.0540 (4)	0.0037 (3)	0.0124 (3)	−0.0015 (3)
S2	0.0501 (4)	0.0523 (4)	0.0540 (4)	0.0045 (3)	0.0146 (3)	0.0007 (3)
S3	0.0488 (4)	0.0529 (4)	0.0534 (4)	0.0041 (3)	0.0141 (3)	−0.0008 (3)
S4	0.0503 (4)	0.0528 (4)	0.0531 (4)	0.0035 (3)	0.0135 (3)	−0.0010 (3)

Geometric parameters (Å, º) top

C1—N1	1.335 (4)	C14—N2	1.314 (4)
C1—C2	1.348 (4)	C14—H14A	0.9599
C1—H1A	0.9601	C15—N2	1.430 (4)
C2—C3	1.340 (4)	C15—C16	1.502 (4)
C2—H2A	0.9600	C15—H15A	0.9601
C3—C4	1.331 (4)	C15—H15B	0.9599
C3—H3A	0.9599	C16—O3	1.163 (3)
C4—C5	1.372 (5)	C16—O4	1.338 (4)
C4—H4A	0.9600	C17—O4	1.471 (4)
C5—N1	1.338 (4)	C17—C18	1.478 (5)
C5—H5A	0.9601	C17—H17A	0.9600
C6—N1	1.450 (4)	C17—H17B	0.9598
C6—C7	1.506 (4)	C18—H18A	0.9600
C6—H6A	0.9600	C18—H18B	0.9600
C6—H6B	0.9599	C18—H18C	0.9600
C7—O1	1.200 (4)	C19—C21	1.349 (4)
C7—O2	1.271 (4)	C19—C20	1.417 (4)
C8—C9	1.482 (5)	C19—S1	1.723 (3)
C8—O2	1.572 (4)	C20—N3	1.148 (4)
C8—H8A	0.9600	C21—C22	1.422 (4)
C8—H8B	0.9600	C21—S2	1.737 (3)
C9—H9A	0.9600	C22—N4	1.132 (4)
C9—H9B	0.9600	C23—C25	1.358 (4)
C9—H9C	0.9600	C23—C24	1.435 (4)
C10—N2	1.325 (4)	C23—S3	1.719 (3)
C10—C11	1.375 (5)	C24—N5	1.138 (4)
C10—H10A	0.9600	C25—C26	1.415 (4)
C11—C12	1.369 (5)	C25—S4	1.730 (3)
C11—H11A	0.9600	C26—N6	1.136 (4)
C12—C13	1.310 (5)	Ni1—S4	2.1599 (9)
C12—H12A	0.9601	Ni1—S2	2.1636 (9)
C13—C14	1.329 (4)	Ni1—S1	2.1647 (9)
C13—H13A	0.9600	Ni1—S3	2.1714 (9)

N1—C1—C2	120.2 (3)	C16—C15—H15A	110.0
N1—C1—H1A	119.7	N2—C15—H15B	108.1
C2—C1—H1A	120.1	C16—C15—H15B	109.4
C3—C2—C1	120.4 (3)	H15A—C15—H15B	108.4
C3—C2—H2A	119.7	O3—C16—O4	125.5 (3)
C1—C2—H2A	119.9	O3—C16—C15	126.4 (3)
C4—C3—C2	120.0 (3)	O4—C16—C15	108.1 (2)
C4—C3—H3A	120.1	O4—C17—C18	106.1 (2)
C2—C3—H3A	119.8	O4—C17—H17A	109.7
C3—C4—C5	119.5 (3)	C18—C17—H17A	109.9
C3—C4—H4A	121.0	O4—C17—H17B	112.1
C5—C4—H4A	119.4	C18—C17—H17B	109.7
N1—C5—C4	120.1 (3)	H17A—C17—H17B	109.3
N1—C5—H5A	119.2	C17—C18—H18A	112.8
C4—C5—H5A	120.6	C17—C18—H18B	107.7
N1—C6—C7	114.1 (3)	H18A—C18—H18B	109.5
N1—C6—H6A	107.8	C17—C18—H18C	107.9
C7—C6—H6A	108.0	H18A—C18—H18C	109.5
N1—C6—H6B	109.2	H18B—C18—H18C	109.5
C7—C6—H6B	109.5	C21—C19—C20	120.3 (3)
H6A—C6—H6B	108.0	C21—C19—S1	119.6 (2)
O1—C7—O2	127.2 (3)	C20—C19—S1	120.1 (2)
O1—C7—C6	121.4 (3)	N3—C20—C19	178.8 (4)
O2—C7—C6	111.2 (3)	C19—C21—C22	120.5 (3)
C9—C8—O2	96.4 (3)	C19—C21—S2	121.3 (2)
C9—C8—H8A	104.2	C22—C21—S2	118.1 (2)
O2—C8—H8A	110.7	N4—C22—C21	178.1 (4)
C9—C8—H8B	116.9	C25—C23—C24	121.1 (3)
O2—C8—H8B	115.5	C25—C23—S3	121.4 (2)
H8A—C8—H8B	111.7	C24—C23—S3	117.4 (2)
C8—C9—H9A	108.3	N5—C24—C23	178.6 (4)
C8—C9—H9B	108.8	C23—C25—C26	122.1 (3)
H9A—C9—H9B	109.5	C23—C25—S4	119.8 (2)
C8—C9—H9C	111.3	C26—C25—S4	117.9 (2)
H9A—C9—H9C	109.5	N6—C26—C25	179.2 (4)
H9B—C9—H9C	109.5	C1—N1—C5	119.8 (3)
N2—C10—C11	119.5 (3)	C1—N1—C6	118.6 (3)
N2—C10—H10A	119.6	C5—N1—C6	121.5 (3)
C11—C10—H10A	120.9	C14—N2—C10	119.7 (3)
C12—C11—C10	118.4 (3)	C14—N2—C15	121.4 (3)
C12—C11—H11A	120.3	C10—N2—C15	119.0 (3)
C10—C11—H11A	121.3	S4—Ni1—S2	176.02 (3)
C13—C12—C11	120.3 (3)	S4—Ni1—S1	88.30 (3)
C13—C12—H12A	120.5	S2—Ni1—S1	91.58 (3)
C11—C12—H12A	119.2	S4—Ni1—S3	91.96 (3)
C12—C13—C14	119.5 (3)	S2—Ni1—S3	88.28 (3)
C12—C13—H13A	119.0	S1—Ni1—S3	178.30 (3)
C14—C13—H13A	121.5	C7—O2—C8	119.8 (2)
N2—C14—C13	122.5 (3)	C16—O4—C17	114.6 (2)
N2—C14—H14A	117.9	C19—S1—Ni1	104.30 (11)
C13—C14—H14A	119.6	C21—S2—Ni1	103.18 (11)
N2—C15—C16	111.5 (2)	C23—S3—Ni1	103.07 (10)
N2—C15—H15A	109.4	C25—S4—Ni1	103.71 (10)

N1—C1—C2—C3	0.5 (5)	C13—C14—N2—C10	−3.8 (5)
C1—C2—C3—C4	0.9 (6)	C13—C14—N2—C15	176.6 (3)
C2—C3—C4—C5	−2.1 (6)	C11—C10—N2—C14	3.5 (5)
C3—C4—C5—N1	2.1 (6)	C11—C10—N2—C15	−176.9 (3)
N1—C6—C7—O1	7.7 (5)	C16—C15—N2—C14	−79.4 (4)
N1—C6—C7—O2	−176.5 (3)	C16—C15—N2—C10	101.0 (4)
N2—C10—C11—C12	−0.7 (5)	O1—C7—O2—C8	15.0 (6)
C10—C11—C12—C13	−2.0 (5)	C6—C7—O2—C8	−160.4 (3)
C11—C12—C13—C14	1.8 (5)	C9—C8—O2—C7	−107.1 (3)
C12—C13—C14—N2	1.1 (5)	O3—C16—O4—C17	2.3 (5)
N2—C15—C16—O3	7.5 (5)	C15—C16—O4—C17	−177.4 (3)
N2—C15—C16—O4	−172.8 (3)	C18—C17—O4—C16	157.6 (3)
C20—C19—C21—C22	3.0 (5)	C21—C19—S1—Ni1	0.1 (3)
S1—C19—C21—C22	−175.5 (3)	C20—C19—S1—Ni1	−178.4 (2)
C20—C19—C21—S2	179.8 (2)	S4—Ni1—S1—C19	174.96 (12)
S1—C19—C21—S2	1.3 (4)	C19—C21—S2—Ni1	−2.0 (3)
C24—C23—C25—C26	8.0 (5)	S1—Ni1—S2—C21	1.54 (12)
S3—C23—C25—C26	−175.3 (3)	S3—Ni1—S2—C21	179.84 (12)
C24—C23—C25—S4	−177.9 (2)	C25—C23—S3—Ni1	−0.2 (3)
C2—C1—N1—C5	−0.5 (5)	C24—C23—S3—Ni1	176.6 (2)
C2—C1—N1—C6	−178.8 (3)	S4—Ni1—S3—C23	1.13 (11)
C4—C5—N1—C1	−0.8 (5)	C23—C25—S4—Ni1	2.0 (3)
C4—C5—N1—C6	177.4 (3)	C26—C25—S4—Ni1	176.3 (2)
C7—C6—N1—C1	−80.3 (4)	S1—Ni1—S4—C25	176.70 (12)
C7—C6—N1—C5	101.4 (4)	S3—Ni1—S4—C25	−1.61 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O1ⁱ	0.96	2.13	3.064 (4)	164
C13—H13A···N6ⁱⁱ	0.96	2.57	3.357 (4)	140
C15—H15B···S2	0.96	2.86	3.680 (3)	145

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

Experimental details

Crystal data
Chemical formula	(C₉H₁₂NO₂)₂[Ni(C₄N₂S₂)₂]
M_r	671.46
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	9.486 (2), 19.542 (5), 17.635 (4)
β (°)	104.803 (4)
V (Å³)	3160.6 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.92
Crystal size (mm)	0.30 × 0.15 × 0.10

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.770, 0.914
No. of measured, independent and observed [I > 2σ(I)] reflections	16888, 6200, 5024
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.114, 1.02
No. of reflections	6200
No. of parameters	370
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.34

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O1ⁱ	0.96	2.13	3.064 (4)	164
C13—H13A···N6ⁱⁱ	0.96	2.57	3.357 (4)	140
C15—H15B···S2	0.96	2.86	3.680 (3)	145

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

Acknowledgements

This work was supported by a project of the Natural Science Foundation of Jiangsu Province (BK2011168) and the Economic and Social Development Foundation of Wuxi (CSZ01010).

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