Bis(1-amino-4-methyl­pyridinium) bis­(1,2-dicyano­ethene-1,2-dithiol­ato-κ2S,S′)nickelate(II)

Liu, J.-L.; Yao, B.-Q.; Zhang, S.-M.

doi:10.1107/S1600536808018886

metal-organic compounds

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Volume 64| Part 7| July 2008| Page m970

doi:10.1107/S1600536808018886

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Bis(1-amino-4-methylpyridinium) bis(1,2-dicyanoethene-1,2-dithiolato-κ²S,S′)nickelate(II)

Jian-Lan Liu,^a Bing-Qian Yao ^a and Shao-Ming Zhang ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: powdtech@njut.edu.cn

(Received 18 June 2008; accepted 23 June 2008; online 28 June 2008)

The asymmetric unit of the title compound, (C₆H₉N₂)₂[Ni(C₄N₂S₂)₂], contains one half of an [Ni(mnt)₂]²⁻ anion (mnt is maleonitriledithiolate or 1,2-dicyanoethene-1,2-dithiolate) and one 1-amino-4-methylpyridinium cation. The Ni^II atom is located on an inversion centre. In the crystal structure, intermolecular N—H⋯N hydrogen bonds link the molecules.

Related literature

For general background, see: Cassoux et al. (1991 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

(C₆H₉N₂)₂[Ni(C₄N₂S₂)₂]
M_r = 557.39
Triclinic, $[P \overline 1]$
a = 7.678 (5) Å
b = 9.095 (6) Å
c = 9.665 (6) Å
α = 93.116 (7)°
β = 104.519 (8)°
γ = 108.813 (7)°
V = 611.7 (7) Å³
Z = 1
Mo Kα radiation
μ = 1.16 mm⁻¹
T = 296 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.732, T_max = 0.892
3040 measured reflections
2097 independent reflections
1937 reflections with I > 2σ(I)
R_int = 0.137

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.173
S = 1.04
2097 reflections
152 parameters
H-atom parameters constrained
Δρ_max = 0.82 e Å⁻³
Δρ_min = −1.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯N1ⁱ	0.86	2.35	3.151 (6)	155
N4—H4B⋯N2	0.86	2.58	3.075 (5)	118
Symmetry code: (i) -x+1, -y+1, -z.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT=; 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: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808018886/hk2475sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808018886/hk2475Isup2.hkl

checkCIF report

Comment top

Square-planar M[dithiolene]₂ complexes have attracted extensive interests in the areas of conducting and magnetic materials, dyes, non-linear optics and catalysis (Cassoux et al., 1991). We report herein the crystal structure of the title compound, (I).

The asymmetric unit of (I) (Fig. 1) contains one-half [Ni(mnt)₂]^2- anion (where mnt is maleonitriledithiolate) and one 1-amino-4-methyl- pyridinium cation. The Ni^II atom is located at the inversion centre. The bond lengths (Allen et al., 1987) and angles are within normal ranges.

In the crystal structure, intra- and intermolecular N-H···N hydrogen bonds (Table 2) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For general background, see: Cassoux et al. (1991). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, disodium maleonitriledithiolate (456 mg, 2.5 mmol) and nickel chloride hexahydrate (297 mg, 1.25 mmol) were mixed with water (20 ml) by stirring at room temperature. Subsequently, a solution of 1-amino-4-methylpyridinium iodide (590 mg, 2.5 mmol) in water (10 ml) was added to the mixture, and the red precipitate immediately formed was filtered off, and washed with water. The crude product was recrystallized in acetone (20 ml) to give red crystals. Crystals suitable for X-ray analysis were obtained by diffusing diethyl ether into the solution of (I) in acetone for 6 d. Anal. Calcd.: C, 43.10; H, 3.26; N, 20.10%. Found: C, 43.15; H, 3.29; N, 20.16%. FTIR data (KBr pellets, cm^-1): 3025, 2928, 2920, 2199, 1577, 1490, 1399, 1125.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme [symmetry code: (') -x, -y, -z].
	Fig. 2. A partial packing diagram of (I). Hydrogen bonds are shown as dashed lines [symmetry code: (') -x, -y, -z]. H atoms not involved in hydrogen bonding have been omitted for clarity.

Bis(1-amino-4-methylpyridinium) bis(1,2-dicyanoethene-1,2-dithiolato-κ²S,S')nicklate(II) top

Crystal data top

(C₆H₉N₂)₂[Ni(C₄N₂S₂)₂]	Z = 1
M_r = 557.39	F(000) = 286
Triclinic, P1	D_x = 1.513 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.678 (5) Å	Cell parameters from 2479 reflections
b = 9.095 (6) Å	θ = 2.3–22.2°
c = 9.665 (6) Å	µ = 1.16 mm⁻¹
α = 93.116 (7)°	T = 296 K
β = 104.519 (8)°	Block, red
γ = 108.813 (7)°	0.30 × 0.20 × 0.10 mm
V = 611.7 (7) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2097 independent reflections
Radiation source: sealed tube	1937 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.137
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→9
T_min = 0.732, T_max = 0.892	k = −10→10
3040 measured reflections	l = −11→8

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.173	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.1404P)²] where P = (F_o² + 2F_c²)/3
2097 reflections	(Δ/σ)_max < 0.001
152 parameters	Δρ_max = 0.82 e Å⁻³
0 restraints	Δρ_min = −1.48 e Å⁻³

Crystal data top

(C₆H₉N₂)₂[Ni(C₄N₂S₂)₂]	γ = 108.813 (7)°
M_r = 557.39	V = 611.7 (7) Å³
Triclinic, P1	Z = 1
a = 7.678 (5) Å	Mo Kα radiation
b = 9.095 (6) Å	µ = 1.16 mm⁻¹
c = 9.665 (6) Å	T = 296 K
α = 93.116 (7)°	0.30 × 0.20 × 0.10 mm
β = 104.519 (8)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2097 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1937 reflections with I > 2σ(I)
T_min = 0.732, T_max = 0.892	R_int = 0.137
3040 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.173	H-atom parameters constrained
S = 1.04	Δρ_max = 0.82 e Å⁻³
2097 reflections	Δρ_min = −1.48 e Å⁻³
152 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 > 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
Ni1	0.5000	1.0000	0.0000	0.0326 (2)
S1	0.53316 (12)	0.82630 (9)	−0.14377 (8)	0.0430 (3)
S2	0.62570 (12)	0.89841 (9)	0.18019 (8)	0.0441 (3)
N1	0.3775 (6)	0.6494 (4)	−0.5237 (4)	0.0726 (10)
N2	0.8189 (5)	0.9732 (4)	0.5790 (3)	0.0570 (7)
N3	0.8790 (4)	0.6656 (3)	0.8401 (3)	0.0463 (6)
N4	0.8879 (5)	0.6838 (4)	0.6984 (4)	0.0633 (8)
H4A	0.8169	0.6097	0.6282	0.076*
H4B	0.9644	0.7692	0.6817	0.076*
C1	0.4152 (4)	0.8525 (4)	−0.3142 (3)	0.0390 (6)
C2	0.3924 (5)	0.7418 (4)	−0.4332 (3)	0.0476 (7)
C3	0.6515 (4)	1.0259 (3)	0.3304 (3)	0.0373 (6)
C4	0.7452 (4)	0.9981 (4)	0.4683 (3)	0.0433 (7)
C5	0.8723 (7)	0.6146 (5)	1.2737 (4)	0.0694 (11)
H5A	0.9882	0.6007	1.3268	0.104*
H5B	0.7639	0.5245	1.2731	0.104*
H5C	0.8615	0.7068	1.3187	0.104*
C6	0.8775 (5)	0.6333 (4)	1.1208 (4)	0.0488 (7)
C7	0.7604 (5)	0.5155 (4)	1.0066 (4)	0.0508 (7)
H7	0.6800	0.4223	1.0251	0.061*
C8	0.7615 (5)	0.5345 (4)	0.8667 (4)	0.0511 (8)
H8	0.6802	0.4556	0.7909	0.061*
C9	0.9972 (5)	0.7824 (4)	0.9466 (4)	0.0516 (8)
H9	1.0795	0.8726	0.9252	0.062*
C10	0.9965 (5)	0.7687 (4)	1.0869 (4)	0.0564 (9)
H10	1.0764	0.8509	1.1601	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0304 (3)	0.0274 (3)	0.0316 (3)	0.0051 (2)	0.0022 (2)	−0.0029 (2)
S1	0.0501 (5)	0.0389 (4)	0.0369 (4)	0.0191 (3)	0.0041 (3)	−0.0026 (3)
S2	0.0558 (5)	0.0376 (4)	0.0348 (4)	0.0194 (4)	0.0031 (3)	−0.0010 (3)
N1	0.091 (3)	0.058 (2)	0.0556 (18)	0.0214 (18)	0.0098 (17)	−0.0172 (15)
N2	0.0604 (18)	0.0588 (18)	0.0416 (15)	0.0165 (14)	0.0021 (12)	0.0067 (12)
N3	0.0428 (14)	0.0357 (13)	0.0576 (15)	0.0130 (11)	0.0119 (11)	−0.0003 (11)
N4	0.078 (2)	0.0500 (17)	0.0605 (18)	0.0180 (16)	0.0238 (16)	0.0052 (13)
C1	0.0360 (14)	0.0370 (15)	0.0354 (14)	0.0068 (11)	0.0052 (11)	−0.0055 (11)
C2	0.0506 (18)	0.0385 (16)	0.0421 (16)	0.0100 (13)	0.0029 (13)	−0.0063 (12)
C3	0.0334 (14)	0.0344 (14)	0.0342 (13)	0.0058 (11)	0.0020 (10)	−0.0028 (10)
C4	0.0400 (16)	0.0402 (15)	0.0404 (15)	0.0073 (12)	0.0051 (12)	0.0007 (12)
C5	0.075 (3)	0.064 (3)	0.063 (2)	0.027 (2)	0.0076 (19)	0.0050 (18)
C6	0.0418 (17)	0.0439 (16)	0.0552 (18)	0.0176 (13)	0.0028 (13)	−0.0011 (13)
C7	0.0487 (18)	0.0321 (15)	0.0605 (19)	0.0042 (13)	0.0111 (14)	−0.0011 (13)
C8	0.0461 (18)	0.0336 (15)	0.0620 (19)	0.0060 (13)	0.0085 (14)	−0.0080 (13)
C9	0.0404 (17)	0.0317 (15)	0.071 (2)	0.0030 (12)	0.0104 (15)	−0.0006 (14)
C10	0.0464 (18)	0.0393 (17)	0.063 (2)	0.0053 (14)	−0.0033 (15)	−0.0110 (14)

Geometric parameters (Å, º) top

Ni1—S1	2.1655 (12)	C5—H5C	0.9600
Ni1—S1ⁱ	2.1655 (12)	C6—C10	1.388 (5)
Ni1—S2	2.1738 (11)	C6—C7	1.388 (5)
Ni1—S2ⁱ	2.1738 (11)	C7—C8	1.375 (5)
S1—C1	1.739 (3)	C7—H7	0.9300
S2—C3	1.737 (3)	C8—N3	1.326 (4)
C1—C3ⁱ	1.361 (4)	C8—H8	0.9300
C1—C2	1.423 (4)	C9—N3	1.343 (4)
C2—N1	1.137 (5)	C9—C10	1.369 (5)
C3—C1ⁱ	1.361 (4)	C9—H9	0.9300
C3—C4	1.426 (4)	C10—H10	0.9300
C4—N2	1.149 (4)	N3—N4	1.404 (4)
C5—C6	1.506 (5)	N4—H4A	0.8600
C5—H5A	0.9600	N4—H4B	0.8600
C5—H5B	0.9600

S1—Ni1—S1ⁱ	180.00 (3)	C10—C6—C7	117.0 (3)
S1—Ni1—S2	88.08 (5)	C10—C6—C5	122.0 (3)
S1ⁱ—Ni1—S2	91.92 (5)	C7—C6—C5	121.0 (4)
S1—Ni1—S2ⁱ	91.92 (5)	C8—C7—C6	120.9 (3)
S1ⁱ—Ni1—S2ⁱ	88.08 (5)	C8—C7—H7	119.5
S2—Ni1—S2ⁱ	180.0	C6—C7—H7	119.5
C1—S1—Ni1	103.30 (12)	N3—C8—C7	119.8 (3)
C3—S2—Ni1	103.34 (12)	N3—C8—H8	120.1
C3ⁱ—C1—C2	122.5 (3)	C7—C8—H8	120.1
C3ⁱ—C1—S1	120.5 (2)	N3—C9—C10	120.0 (3)
C2—C1—S1	117.0 (3)	N3—C9—H9	120.0
N1—C2—C1	176.8 (4)	C10—C9—H9	120.0
C1ⁱ—C3—C4	122.4 (3)	C9—C10—C6	120.6 (3)
C1ⁱ—C3—S2	120.3 (2)	C9—C10—H10	119.7
C4—C3—S2	117.4 (2)	C6—C10—H10	119.7
N2—C4—C3	178.9 (4)	C8—N3—C9	121.7 (3)
C6—C5—H5A	109.5	C8—N3—N4	120.4 (3)
C6—C5—H5B	109.5	C9—N3—N4	117.8 (3)
H5A—C5—H5B	109.5	N3—N4—H4A	120.0
C6—C5—H5C	109.5	N3—N4—H4B	120.0
H5A—C5—H5C	109.5	H4A—N4—H4B	120.0
H5B—C5—H5C	109.5

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N1ⁱⁱ	0.86	2.35	3.151 (6)	155
N4—H4B···N2	0.86	2.58	3.075 (5)	118

Symmetry code: (ii) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	(C₆H₉N₂)₂[Ni(C₄N₂S₂)₂]
M_r	557.39
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.678 (5), 9.095 (6), 9.665 (6)
α, β, γ (°)	93.116 (7), 104.519 (8), 108.813 (7)
V (Å³)	611.7 (7)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.16
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.732, 0.892
No. of measured, independent and observed [I > 2σ(I)] reflections	3040, 2097, 1937
R_int	0.137
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.173, 1.04
No. of reflections	2097
No. of parameters	152
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.82, −1.48

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N1ⁱ	0.86	2.35	3.151 (6)	155.2
N4—H4B···N2	0.86	2.58	3.075 (5)	117.7

Symmetry code: (i) −x+1, −y+1, −z.

Acknowledgements

The authors thank the Science and Technology Department of Jiangsu Province, People's Republic of China, and the Natural Science Foundation of China for financial support (grant No. 10774076).

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cassoux, P., Valade, L., Kobayashi, H., Kobayashi, A., Clark, R. A. & Underhill, A. E. (1991). Coord. Chem. Rev. 110, 115–160. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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