3,3′-Dimethyl-1,1′-(propane-1,3-di­yl)diimidazol-1-ium bis­(1,2-dicyano­ethene-1,2-dithiol­ato-κ2S,S′)nickelate(II)

Yu, S.-S.; Duan, H.-B.; Ren, X.-M.

doi:10.1107/S1600536811027693

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page m1117

doi:10.1107/S1600536811027693

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3,3′-Dimethyl-1,1′-(propane-1,3-diyl)diimidazol-1-ium bis(1,2-dicyanoethene-1,2-dithiolato-κ²S,S′)nickelate(II)

Shan-Shan Yu,^a Hai-Bao Duan ^b ^* and Xiao-Ming Ren ^c

^aDepartment of Chemistry, Nanjing Xiaozhuang College, Nanjing 210017, People's Republic of China, ^bSchool of Biochemical and Environmental Engineering, Nanjing Xiaozhuang College, Nanjing 210017, People's Republic of China, and ^cCollege of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: duanhaibao4660@163.com

(Received 4 June 2011; accepted 11 July 2011; online 23 July 2011)

In the title compound, (C₁₁H₁₈N₄)[Ni(C₄N₂S₂)₂], the asymmetric contains one half-complex, with the cation placed on a twofold axis and the anion located on an inversion center. The Ni^II ion in the anion is coordinated by four S atoms of two maleonitriledithiolate ligands, and exhibits the expected square-planar coordination geometry.

Related literature

For the design of functional materials, see: Robertson & Cronin (2002 ). For near-infrared dyes, conducting, magnetic and non-linear optical materials, see: Nishijo et al. (2000 ); 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 the title compound, see: Davison & Holm (1967 ); Yao et al. (2008 ).

Experimental

Crystal data

(C₁₁H₁₈N₄)[Ni(C₄N₂S₂)₂]
M_r = 545.38
Monoclinic, C 2/c
a = 19.3683 (15) Å
b = 7.3026 (6) Å
c = 17.5170 (14) Å
β = 104.167 (1)°
V = 2402.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.18 mm⁻¹
T = 293 K
0.4 × 0.3 × 0.3 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.702, T_max = 0.741
7551 measured reflections
2938 independent reflections
2503 reflections with I > 2σ(I)
R_int = 0.067

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.101
S = 1.06
2938 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; 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/S1600536811027693/bh2362sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811027693/bh2362Isup2.hkl

checkCIF report

Comment top

Supramolecular chemistry and molecular crystal engineering, which is the planning and utilization of crystal-oriented syntheses for the bottom-up construction of functional molecular solids from molecules and ions, are powerful tools for the assembly of designed functional materials (Robertson & Cronin, 2002). The use of bis-1,2-dithiolene complexes of transition metals as building units in the construction of such molecule based materials has received extensive attention due to their potential applications in the areas of near-infrared (near-IR) dyes, conducting, magnetic and nonlinear optical materials (Nishijo et al., 2000; Ni et al., 2005). Herein we report the crystal structure of the title compound (Fig. 1), which belongs to this class of materials.

The compound crystallizes in monoclinic system, with one half of [Ni(mnt)₂]^2- dianion (mnt = maleonitriledithiolate) and one half of 3,3-dimethyl-1,1-(propane-1,3-diyl)diimidazol-1-ium dication in the asymmetric unit. The Ni center in the [Ni(mnt)₂]^2- anion is coordinated by four S atoms of two mnt^2- ligands, and exhibits the expected square-planar coordination geometry. The bond lengths and angles in the anion are in good agreement with those observed in other [Ni(mnt)₂]^2- complexes (Ni et al., 2004; Ren et al., 2004, 2008; Duan et al., 2010).

Related literature top

For the design of functional materials, see: Robertson & Cronin (2002). For near-infrared dyes, conducting, magnetic and non-linear optical materials, see: Nishijo et al. (2000); 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 the title compound, see: Davison & Holm (1967); Yao et al. (2008).

Experimental top

All reagents and chemicals were purchased from commercial sources and used without further purification. The starting materials disodium maleonitriledithiolate and 1-methyl-3-(3-(1-methyl-imidazole-3-yl)propyl)-imidazolinium iodide were synthesized following the literature procedures (Davison & Holm, 1967; Yao et al., 2008). Disodium maleonitriledithiolate (456 mg, 2.5 mmol) and nickel chloride hexahydrate (297 mg, 1.25 mmol) were mixed under stirring in water (20 ml) at room temperature. Subsequently, a solution of 1-methyl-3-(3-(1-methyl-imidazole-3-yl)propyl)-imidazolinium iodide (1.5 mmol) in methanol (10 ml) was added to the mixture, and the red precipitate that immediately formed was filtered off, and washed with methanol. The crude product was recrystallized in acetone (20 ml) to give red block crystals.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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. The molecular structure of the title compound, showing displacement ellipsoids at the 30% probability level.

3,3'-Dimethyl-1,1'-(propane-1,3-diyl)diimidazol-1-ium bis(1,2-dicyanoethene-1,2-dithiolato-κ²S,S')nickelate(II) top

Crystal data top

(C₁₁H₁₈N₄)[Ni(C₄N₂S₂)₂]	Z = 4
M_r = 545.38	F(000) = 1120.0
Monoclinic, C2/c	D_x = 1.508 Mg m⁻³
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 19.3683 (15) Å	µ = 1.18 mm⁻¹
b = 7.3026 (6) Å	T = 293 K
c = 17.5170 (14) Å	Block, red
β = 104.167 (1)°	0.4 × 0.3 × 0.3 mm
V = 2402.2 (3) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2938 independent reflections
Radiation source: fine-focus sealed tube	2503 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.067
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −19→25
T_min = 0.702, T_max = 0.741	k = −8→9
7551 measured reflections	l = −23→16

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0544P)² + 0.2056P] where P = (F_o² + 2F_c²)/3
2938 reflections	(Δ/σ)_max < 0.001
147 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.68 e Å⁻³

Crystal data top

(C₁₁H₁₈N₄)[Ni(C₄N₂S₂)₂]	V = 2402.2 (3) Å³
M_r = 545.38	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 19.3683 (15) Å	µ = 1.18 mm⁻¹
b = 7.3026 (6) Å	T = 293 K
c = 17.5170 (14) Å	0.4 × 0.3 × 0.3 mm
β = 104.167 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2938 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	2503 reflections with I > 2σ(I)
T_min = 0.702, T_max = 0.741	R_int = 0.067
7551 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.06	Δρ_max = 0.31 e Å⁻³
2938 reflections	Δρ_min = −0.68 e Å⁻³
147 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni1	0.2500	0.7500	0.0000	0.03604 (12)
S1	0.34431 (2)	0.65936 (7)	0.08669 (3)	0.04682 (15)
S2	0.18479 (2)	0.72779 (7)	0.08353 (3)	0.04539 (14)
N1	0.40853 (10)	0.5664 (3)	0.29918 (11)	0.0762 (6)
N2	0.19161 (11)	0.6190 (3)	0.28956 (11)	0.0698 (5)
N3	0.61640 (10)	0.7743 (2)	1.00222 (10)	0.0491 (4)
N4	0.54547 (9)	0.8708 (2)	0.89552 (10)	0.0576 (4)
C1	0.36589 (10)	0.5949 (3)	0.24289 (11)	0.0516 (4)
C2	0.31437 (9)	0.6359 (2)	0.17168 (10)	0.0416 (4)
C3	0.24477 (9)	0.6629 (2)	0.17021 (10)	0.0401 (4)
C4	0.21663 (10)	0.6392 (3)	0.23745 (11)	0.0492 (4)
C5	0.61229 (10)	0.8655 (3)	0.93644 (11)	0.0475 (4)
H5A	0.6506	0.9180	0.9212	0.057*
C6	0.68163 (15)	0.7392 (3)	1.06347 (14)	0.0661 (7)
H6A	0.7213	0.7962	1.0491	0.099*
H6B	0.6896	0.6096	1.0689	0.099*
H6C	0.6767	0.7889	1.1126	0.099*
C7	0.55032 (15)	0.7161 (4)	1.00398 (16)	0.0803 (8)
H7A	0.5380	0.6474	1.0434	0.096*
C8	0.50654 (15)	0.7773 (5)	0.9379 (2)	0.0919 (10)
H8A	0.4575	0.7592	0.9231	0.110*
C9	0.52021 (13)	0.9711 (3)	0.82143 (13)	0.0750 (7)
H9A	0.5573	1.0547	0.8150	0.090*
H9B	0.4792	1.0439	0.8248	0.090*
C10	0.5000	0.8508 (4)	0.7500	0.0559 (7)
H10A	0.4602	0.7731	0.7532	0.067*	0.50
H10B	0.5398	0.7731	0.7468	0.067*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.03490 (18)	0.03872 (19)	0.03238 (19)	−0.00051 (11)	0.00419 (13)	−0.00245 (11)
S1	0.0380 (2)	0.0625 (3)	0.0377 (2)	0.00491 (19)	0.00505 (18)	0.0005 (2)
S2	0.0379 (2)	0.0577 (3)	0.0397 (3)	0.00376 (18)	0.00789 (19)	0.00350 (19)
N1	0.0665 (12)	0.1072 (17)	0.0468 (10)	0.0188 (12)	−0.0018 (9)	0.0070 (11)
N2	0.0691 (11)	0.0954 (14)	0.0488 (10)	0.0063 (11)	0.0220 (9)	0.0090 (10)
N3	0.0537 (9)	0.0483 (9)	0.0413 (9)	−0.0086 (7)	0.0039 (7)	−0.0020 (7)
N4	0.0479 (9)	0.0663 (10)	0.0497 (9)	−0.0038 (8)	−0.0049 (7)	−0.0074 (8)
C1	0.0493 (10)	0.0627 (11)	0.0406 (9)	0.0054 (9)	0.0065 (8)	−0.0019 (9)
C2	0.0462 (9)	0.0413 (8)	0.0344 (8)	0.0003 (7)	0.0042 (7)	−0.0017 (7)
C3	0.0459 (9)	0.0382 (8)	0.0346 (8)	−0.0023 (7)	0.0069 (7)	−0.0022 (7)
C4	0.0503 (10)	0.0539 (10)	0.0423 (10)	0.0019 (8)	0.0091 (8)	0.0012 (8)
C5	0.0454 (9)	0.0498 (10)	0.0423 (10)	−0.0046 (8)	0.0012 (7)	0.0019 (8)
C6	0.0740 (15)	0.0568 (13)	0.0549 (14)	0.0002 (10)	−0.0086 (12)	0.0085 (9)
C7	0.0686 (16)	0.112 (2)	0.0614 (15)	−0.0278 (15)	0.0177 (13)	0.0053 (14)
C8	0.0446 (12)	0.140 (3)	0.087 (2)	−0.0210 (14)	0.0079 (13)	0.0053 (19)
C9	0.0783 (15)	0.0643 (13)	0.0611 (13)	0.0102 (12)	−0.0238 (12)	−0.0046 (11)
C10	0.0481 (14)	0.0592 (17)	0.0525 (16)	0.000	−0.0027 (12)	0.000

Geometric parameters (Å, º) top

Ni1—S2ⁱ	2.1603 (5)	C2—C3	1.356 (3)
Ni1—S2	2.1603 (5)	C3—C4	1.424 (3)
Ni1—S1	2.1732 (4)	C5—H5A	0.9300
Ni1—S1ⁱ	2.1732 (4)	C6—H6A	0.9600
S1—C2	1.7334 (18)	C6—H6B	0.9600
S2—C3	1.7369 (17)	C6—H6C	0.9600
N1—C1	1.140 (2)	C7—C8	1.334 (4)
N2—C4	1.143 (3)	C7—H7A	0.9300
N3—C5	1.316 (2)	C8—H8A	0.9300
N3—C7	1.356 (3)	C9—C10	1.500 (3)
N3—C6	1.466 (3)	C9—H9A	0.9700
N4—C5	1.318 (2)	C9—H9B	0.9700
N4—C8	1.364 (4)	C10—C9ⁱⁱ	1.500 (3)
N4—C9	1.466 (3)	C10—H10A	0.9700
C1—C2	1.426 (2)	C10—H10B	0.9700

S2ⁱ—Ni1—S2	180.00 (3)	N3—C6—H6A	109.5
S2ⁱ—Ni1—S1	88.018 (18)	N3—C6—H6B	109.5
S2—Ni1—S1	91.983 (18)	H6A—C6—H6B	109.5
S2ⁱ—Ni1—S1ⁱ	91.983 (18)	N3—C6—H6C	109.5
S2—Ni1—S1ⁱ	88.017 (18)	H6A—C6—H6C	109.5
S1—Ni1—S1ⁱ	180.000 (17)	H6B—C6—H6C	109.5
C2—S1—Ni1	103.27 (6)	C8—C7—N3	106.2 (2)
C3—S2—Ni1	103.64 (6)	C8—C7—H7A	126.9
C5—N3—C7	108.85 (19)	N3—C7—H7A	126.9
C5—N3—C6	125.85 (19)	C7—C8—N4	108.8 (2)
C7—N3—C6	125.3 (2)	C7—C8—H8A	125.6
C5—N4—C8	106.8 (2)	N4—C8—H8A	125.6
C5—N4—C9	124.5 (2)	N4—C9—C10	114.08 (19)
C8—N4—C9	128.5 (2)	N4—C9—H9A	108.7
N1—C1—C2	177.7 (2)	C10—C9—H9A	108.7
C3—C2—C1	121.79 (17)	N4—C9—H9B	108.7
C3—C2—S1	120.62 (13)	C10—C9—H9B	108.7
C1—C2—S1	117.55 (14)	H9A—C9—H9B	107.6
C2—C3—C4	123.12 (16)	C9—C10—C9ⁱⁱ	108.3 (3)
C2—C3—S2	120.34 (14)	C9—C10—H10A	110.0
C4—C3—S2	116.53 (14)	C9ⁱⁱ—C10—H10A	110.0
N2—C4—C3	177.4 (2)	C9—C10—H10B	110.0
N3—C5—N4	109.39 (19)	C9ⁱⁱ—C10—H10B	110.0
N3—C5—H5A	125.3	H10A—C10—H10B	108.4
N4—C5—H5A	125.3

Symmetry codes: (i) −x+1/2, −y+3/2, −z; (ii) −x+1, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	(C₁₁H₁₈N₄)[Ni(C₄N₂S₂)₂]
M_r	545.38
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	19.3683 (15), 7.3026 (6), 17.5170 (14)
β (°)	104.167 (1)
V (Å³)	2402.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.18
Crystal size (mm)	0.4 × 0.3 × 0.3

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.702, 0.741
No. of measured, independent and observed [I > 2σ(I)] reflections	7551, 2938, 2503
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.101, 1.06
No. of reflections	2938
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.68

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank the Natural Science Foundation of High Learning Institutions of Abhui Province, China for financial support (grant Nos. KJ2009B275Z).

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