1-Butyl-pyridinium bis-(1,2-dicyano-ethene-1,2-dithiol-ato)nickelate(III).

The Ni(III) atom in the anion of the title complex, (C(9)H(14)N)[Ni(C(4)N(2)S(2))(2)], is coordinated by four S atoms of two maleonitrile-dithiol-ate ligands, and exhibits a square-planar coordination geometry.

Related literature

For background to designed functional materials, see: Nishijo et al. (2000 ▶); Robertson & Cronin (2002 ▶); Ni et al. (2005 ▶). For related structures, see: Ni et al. (2004 ▶); Ren et al. (2004 ▶, 2008 ▶); Duan et al. (2010 ▶). For the synthesis of disodium maleonitrile­dithiol­ate and 1-butane-pyridinium bromide, see: Davison & Holm (1967 ▶); Yao et al. (2008 ▶).

Experimental

Crystal data

(C9H14N)[Ni(C4N2S2)2]

M = 475.30

Triclinic,

a = 9.2764 (11) Å

b = 9.9863 (11) Å

c = 12.7115 (15) Å

α = 81.695 (9)°

β = 75.882 (10)°

γ = 64.480 (11)°

V = 1029.5 (2) Å3

Z = 2

Cu Kα radiation

μ = 5.25 mm−1

T = 293 K

0.3 × 0.1 × 0.1 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2002) ▶ T min = 0.559, T max = 0.591

7461 measured reflections

3196 independent reflections

2499 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.109

S = 1.04

3196 reflections

245 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.33 e Å−3

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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811042103/tk2798sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811042103/tk2798Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C9H14N)[Ni(C4N2S2)2]	V = 1029.5 (2) Å3
Mr = 475.30	Z = 2
Triclinic, P1	F(000) = 486
Hall symbol: -P 1	Dx = 1.533 Mg m−3
a = 9.2764 (11) Å	Cu Kα radiation, λ = 1.54178 Å
b = 9.9863 (11) Å	µ = 5.25 mm−1
c = 12.7115 (15) Å	T = 293 K
α = 81.695 (9)°	Block, black
β = 75.882 (10)°	0.3 × 0.1 × 0.1 mm
γ = 64.480 (11)°

Bruker SMART CCD area-detector diffractometer	3196 independent reflections
Radiation source: fine-focus sealed tube	2499 reflections with I > 2σ(I)
graphite	Rint = 0.018
φ and ω scans	θmax = 62.6°, θmin = 3.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −10→9
Tmin = 0.559, Tmax = 0.591	k = −11→11
7461 measured reflections	l = −14→12

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0752P)2] where P = (Fo2 + 2Fc2)/3
3196 reflections	(Δ/σ)max < 0.001
245 parameters	Δρmax = 0.36 e Å−3
1 restraint	Δρmin = −0.33 e Å−3

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.

	x	y	z	Uiso*/Ueq
Ni1	0.17351 (5)	0.21297 (4)	0.32522 (3)	0.05459 (18)
S1	−0.01043 (8)	0.19088 (7)	0.45807 (6)	0.0601 (2)
S2	0.04693 (8)	0.45024 (7)	0.31675 (6)	0.0634 (2)
S3	0.34944 (8)	0.23715 (8)	0.18766 (6)	0.0646 (2)
S4	0.30030 (9)	−0.02462 (7)	0.33157 (6)	0.0681 (2)
N1	−0.3268 (3)	0.7577 (3)	0.4479 (2)	0.0791 (7)
N2	−0.4145 (3)	0.4193 (3)	0.6218 (2)	0.0862 (8)
N3	0.6747 (3)	−0.3235 (3)	0.1797 (2)	0.0886 (8)
N4	0.7294 (3)	0.0134 (3)	0.0023 (2)	0.0882 (8)
N5	0.1415 (3)	0.7746 (2)	0.81191 (17)	0.0575 (5)
C1	−0.2966 (3)	0.3967 (3)	0.5591 (2)	0.0611 (7)
C2	−0.1507 (3)	0.3709 (3)	0.4772 (2)	0.0531 (6)
C3	−0.2387 (3)	0.6364 (3)	0.4331 (2)	0.0599 (7)
C4	−0.1257 (3)	0.4844 (3)	0.4169 (2)	0.0550 (6)
C5	0.6208 (3)	0.0325 (3)	0.0733 (2)	0.0652 (7)
C6	0.4856 (3)	0.0568 (3)	0.1630 (2)	0.0565 (6)
C7	0.4645 (3)	−0.0567 (3)	0.2251 (2)	0.0569 (6)
C8	0.5794 (3)	−0.2072 (3)	0.2023 (2)	0.0659 (7)
C9	0.2814 (3)	0.6993 (3)	0.7434 (2)	0.0650 (7)
H9	0.3298	0.5961	0.7497	0.078*
C10	0.3530 (4)	0.7722 (3)	0.6651 (2)	0.0731 (8)
H10	0.4497	0.7186	0.6182	0.088*
C11	0.2837 (4)	0.9231 (4)	0.6549 (2)	0.0777 (9)
H11	0.3331	0.9734	0.6020	0.093*
C12	0.1386 (4)	1.0006 (3)	0.7248 (3)	0.0782 (9)
H12	0.0884	1.1037	0.7190	0.094*
C13	0.0705 (4)	0.9233 (3)	0.8022 (2)	0.0686 (8)
H13	−0.0272	0.9748	0.8491	0.082*
C14	0.0666 (4)	0.6954 (3)	0.8999 (2)	0.0675 (7)
H14A	0.1108	0.5915	0.8837	0.081*
H14B	−0.0502	0.7374	0.9038	0.081*
C15	0.0995 (4)	0.7078 (4)	1.0100 (2)	0.0785 (9)
H15A	0.0642	0.8119	1.0222	0.094*
H15B	0.0340	0.6697	1.0668	0.094*
C16	0.2730 (4)	0.6270 (4)	1.0199 (3)	0.0827 (9)
H16A	0.3399	0.6628	0.9625	0.099*
H16B	0.3082	0.5220	1.0108	0.099*
C17	0.2978 (4)	0.6479 (4)	1.1299 (3)	0.0867 (10)
H17A	0.2674	0.7513	1.1377	0.130*
H17B	0.4104	0.5924	1.1341	0.130*
H17C	0.2311	0.6131	1.1868	0.130*

	U11	U22	U33	U12	U13	U23
Ni1	0.0448 (3)	0.0471 (3)	0.0603 (3)	−0.0124 (2)	−0.0012 (2)	−0.0050 (2)
S1	0.0525 (4)	0.0452 (4)	0.0670 (4)	−0.0135 (3)	0.0015 (3)	−0.0008 (3)
S2	0.0567 (4)	0.0489 (4)	0.0689 (4)	−0.0174 (3)	0.0060 (3)	−0.0021 (3)
S3	0.0525 (4)	0.0501 (4)	0.0736 (4)	−0.0146 (3)	0.0055 (3)	−0.0022 (3)
S4	0.0579 (4)	0.0488 (4)	0.0742 (5)	−0.0127 (3)	0.0096 (4)	−0.0021 (3)
N1	0.0769 (17)	0.0505 (15)	0.0934 (19)	−0.0155 (13)	−0.0048 (14)	−0.0097 (13)
N2	0.0728 (18)	0.0701 (17)	0.0859 (18)	−0.0194 (14)	0.0192 (15)	−0.0071 (14)
N3	0.0788 (18)	0.0535 (16)	0.103 (2)	−0.0110 (14)	0.0082 (15)	−0.0122 (14)
N4	0.0702 (18)	0.0761 (18)	0.0905 (19)	−0.0213 (14)	0.0174 (16)	−0.0071 (15)
N5	0.0505 (12)	0.0568 (13)	0.0561 (12)	−0.0137 (10)	−0.0055 (10)	−0.0116 (10)
C1	0.0588 (17)	0.0468 (14)	0.0640 (16)	−0.0144 (12)	−0.0012 (14)	−0.0049 (12)
C2	0.0487 (14)	0.0487 (14)	0.0529 (13)	−0.0139 (11)	−0.0031 (12)	−0.0079 (11)
C3	0.0610 (17)	0.0499 (17)	0.0608 (15)	−0.0200 (13)	−0.0031 (13)	−0.0034 (12)
C4	0.0512 (15)	0.0477 (14)	0.0581 (14)	−0.0143 (11)	−0.0040 (12)	−0.0104 (12)
C5	0.0555 (17)	0.0548 (16)	0.0709 (18)	−0.0164 (13)	0.0016 (15)	−0.0049 (13)
C6	0.0425 (14)	0.0557 (15)	0.0617 (15)	−0.0135 (11)	−0.0023 (12)	−0.0097 (12)
C7	0.0469 (14)	0.0512 (15)	0.0615 (15)	−0.0125 (12)	−0.0024 (12)	−0.0091 (12)
C8	0.0583 (17)	0.0542 (17)	0.0709 (17)	−0.0181 (14)	0.0033 (14)	−0.0048 (14)
C9	0.0559 (17)	0.0590 (16)	0.0660 (17)	−0.0105 (13)	−0.0073 (14)	−0.0122 (14)
C10	0.0630 (18)	0.075 (2)	0.0645 (17)	−0.0190 (16)	0.0043 (15)	−0.0130 (15)
C11	0.086 (2)	0.081 (2)	0.0653 (17)	−0.0384 (18)	−0.0079 (17)	0.0008 (16)
C12	0.090 (2)	0.0564 (17)	0.0769 (19)	−0.0210 (16)	−0.0151 (18)	−0.0030 (15)
C13	0.0653 (18)	0.0539 (16)	0.0689 (17)	−0.0092 (14)	−0.0057 (15)	−0.0130 (14)
C14	0.0621 (18)	0.0705 (18)	0.0689 (17)	−0.0297 (15)	−0.0060 (14)	−0.0053 (14)
C15	0.072 (2)	0.078 (2)	0.0735 (18)	−0.0302 (16)	0.0003 (16)	0.0052 (16)
C16	0.083 (2)	0.071 (2)	0.082 (2)	−0.0255 (17)	−0.0114 (18)	0.0043 (16)
C17	0.096 (2)	0.093 (2)	0.079 (2)	−0.046 (2)	−0.0262 (19)	0.0118 (18)

Ni1—S1	2.1501 (8)	C9—C10	1.359 (4)
Ni1—S2	2.1436 (8)	C9—H9	0.9300
Ni1—S3	2.1458 (8)	C10—C11	1.361 (4)
Ni1—S4	2.1461 (8)	C10—H10	0.9300
S1—C2	1.715 (2)	C11—C12	1.384 (4)
S2—C4	1.721 (3)	C11—H11	0.9300
S3—C6	1.717 (3)	C12—C13	1.364 (4)
S4—C7	1.719 (3)	C12—H12	0.9300
N1—C3	1.145 (3)	C13—H13	0.9300
N2—C1	1.139 (4)	C14—C15	1.536 (4)
N3—C8	1.141 (4)	C14—H14A	0.9700
N4—C5	1.143 (3)	C14—H14B	0.9700
N5—C13	1.341 (4)	C15—C16	1.485 (4)
N5—C9	1.344 (3)	C15—H15A	0.9700
N5—C14	1.483 (3)	C15—H15B	0.9700
C1—C2	1.439 (4)	C16—C17	1.527 (5)
C2—C4	1.348 (4)	C16—H16A	0.9700
C3—C4	1.435 (4)	C16—H16B	0.9700
C5—C6	1.432 (4)	C17—H17A	0.9600
C6—C7	1.343 (4)	C17—H17B	0.9600
C7—C8	1.440 (4)	C17—H17C	0.9600
S2—Ni1—S3	86.97 (3)	C11—C10—H10	119.8
S2—Ni1—S4	179.28 (3)	C10—C11—C12	118.9 (3)
S3—Ni1—S4	92.59 (3)	C10—C11—H11	120.6
S2—Ni1—S1	92.34 (3)	C12—C11—H11	120.6
S3—Ni1—S1	177.33 (3)	C13—C12—C11	119.0 (3)
S4—Ni1—S1	88.08 (3)	C13—C12—H12	120.5
C2—S1—Ni1	103.03 (9)	C11—C12—H12	120.5
C4—S2—Ni1	103.36 (9)	N5—C13—C12	121.3 (3)
C6—S3—Ni1	102.87 (10)	N5—C13—H13	119.3
C7—S4—Ni1	102.92 (9)	C12—C13—H13	119.3
C13—N5—C9	119.7 (3)	N5—C14—C15	111.1 (2)
C13—N5—C14	119.5 (2)	N5—C14—H14A	109.4
C9—N5—C14	120.7 (2)	C15—C14—H14A	109.4
N2—C1—C2	178.1 (3)	N5—C14—H14B	109.4
C4—C2—C1	121.1 (2)	C15—C14—H14B	109.4
C4—C2—S1	121.02 (19)	H14A—C14—H14B	108.0
C1—C2—S1	117.88 (19)	C16—C15—C14	114.5 (3)
N1—C3—C4	178.3 (3)	C16—C15—H15A	108.6
C2—C4—C3	122.3 (2)	C14—C15—H15A	108.6
C2—C4—S2	120.21 (19)	C16—C15—H15B	108.6
C3—C4—S2	117.5 (2)	C14—C15—H15B	108.6
N4—C5—C6	179.3 (3)	H15A—C15—H15B	107.6
C7—C6—C5	121.6 (2)	C15—C16—C17	111.7 (3)
C7—C6—S3	120.9 (2)	C15—C16—H16A	109.3
C5—C6—S3	117.5 (2)	C17—C16—H16A	109.3
C6—C7—C8	120.0 (2)	C15—C16—H16B	109.3
C6—C7—S4	120.7 (2)	C17—C16—H16B	109.3
C8—C7—S4	119.3 (2)	H16A—C16—H16B	107.9
N3—C8—C7	176.4 (3)	C16—C17—H17A	109.5
N5—C9—C10	120.7 (3)	C16—C17—H17B	109.5
N5—C9—H9	119.6	H17A—C17—H17B	109.5
C10—C9—H9	119.6	C16—C17—H17C	109.5
C9—C10—C11	120.3 (3)	H17A—C17—H17C	109.5
C9—C10—H10	119.8	H17B—C17—H17C	109.5

Table 1

Selected bond lengths (Å)

Ni1—S1	2.1501 (8)
Ni1—S2	2.1436 (8)
Ni1—S3	2.1458 (8)
Ni1—S4	2.1461 (8)