Bis[1-(4-cyano­benz­yl)pyrazinium] bis­(1,2-dicyano­ethene-1,2-dithiol­ato)nickelate(II)

Zhang, H.; Pei, W.-B.; Yu, S.-S.; Ren, X.-M.

doi:10.1107/S1600536811022550

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page m943

doi:10.1107/S1600536811022550

Open

access

Bis[1-(4-cyanobenzyl)pyrazinium] bis(1,2-dicyanoethene-1,2-dithiolato)nickelate(II)

Hui Zhang,^a Wen-Bo Pei,^a Shan-Shan Yu ^b and Xiao-Ming Ren ^a ^*

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

(Received 5 June 2011; accepted 10 June 2011; online 18 June 2011)

The asymmetric unit of the title complex, (C₁₂H₁₀N₃)₂[Ni(C₄N₂S₂)₂], consists of one 1-(4-cyanobenzyl)pyrazinium cation and one half of an [Ni(mnt)₂]²⁻ dianion (mnt²⁻ is 1,2-dicyanoethene-1,2-dithiolate). The Ni²⁺ ion is located on an inversion center and is coordinated by four S atoms from two mnt²⁻ ligands, exhibiting a square-planar coordination geometry. The cation adopts a conformation where both the pyrazine ring and the benzene ring are twisted with respect to the C—C—N reference plane by 16.5 (2) and 69.8 (1)°, respectively.

Related literature

For general background to square-planar bis-1,2-dithiolato complexes of transition metals showing potential application as magnetic or conducting materials and other properties, see: Bigoli et al. (2002 ); Duan et al. (2010 ); Pei et al. (2011 ). For the synthesis, see: Davison & Holm (1967 ).

Experimental

Crystal data

(C₁₂H₁₀N₃)₂[Ni(C₄N₂S₂)₂]
M_r = 731.53
Monoclinic, P 2₁ /n
a = 7.115 (3) Å
b = 13.623 (6) Å
c = 17.186 (8) Å
β = 101.671 (5)°
V = 1631.4 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.89 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.15 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) T_min = 0.807, T_max = 0.875
8060 measured reflections
2871 independent reflections
2586 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.074
S = 1.06
2871 reflections
214 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); 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 I, global. DOI: 10.1107/S1600536811022550/im2295sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811022550/im2295Isup2.hkl

checkCIF report

Comment top

Bis-1,2-dithiolene complexes of transition metals have been widely studied because of their novel properties and applications in the areas of conducting and magnetic materials, dyes, nonlinear optics, catalysis and others. These applications arise due to a combination of functional properties, specific geometries and intermolecular interactions. (Bigoli et al., 2002; Duan et al., 2010; Pei et al., 2011). Herein we report the crystal structure of the title compound (Fig. 1).

An asymmetric unit consists of one half [Ni(mnt)₂]^2- dianion and one 1-N-(4'-cyano-benzyl)-pyrazinium cation. In the [Ni(mnt)₂]^2- moiety, the Ni atom is situated at a inversion center and is coordinated by four S atoms from two mnt^2- ligands, forming a square-planar coordination geometry. The cation adopts a conformation where the bond lengths and bond angles were normal, and both the pyrazine ring and the phenyl ring are twisted with respect to the C8—C12—N4 reference plane with the corresponding dihedral angles of 16.5 (2)° and 69.8 (1)°.

Related literature top

For general background to square-planar bis-1,2-dithiolene complexes of transition metals showing potential application as magnetic or conducting materials and other properties, see: Bigoli et al. (2002); Duan et al. (2010); Pei et al. (2011). For the synthesis, see: Davison & Holm (1967).

Experimental top

Disodium maleonitriledithiolate (456 mg, 2.5 mmol) and nickel chloride hexahydrate (297 mg, 1.25 mmol) were mixed under stirring in water (20 ml) and heated to boiling for about 20 min. After the red solution was filtered an aqueous solution of 1-N-(4'-cyano-benzyl)-pyrazinium chloride (579 mg, 2.5 mmol) was added dropwise to the filtrate. The immediately formed dark red precipitate was filtered off, washed with water and dried in vacuum (yield: 722 mg, 79%). Block shaped single crystals suitable for X-ray analysis were obtained via recrystallization of the corresponding complex in acetone.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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. Molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level (i = -x, -y, -z).
	Fig. 2. Packing diagram for (I) viewed along a axis.

Bis[1-(4-cyanobenzyl)pyrazinium] bis(1,2-dicyanoethene-1,2-dithiolato)nickelate(II) top

Crystal data top

(C₁₂H₁₀N₃)₂[Ni(C₄N₂S₂)₂]	F(000) = 748
M_r = 731.53	D_x = 1.489 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 456 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 7.115 (3) Å	Cell parameters from 8060 reflections
b = 13.623 (6) Å	θ = 2.4–25.0°
c = 17.186 (8) Å	µ = 0.89 mm⁻¹
β = 101.671 (5)°	T = 298 K
V = 1631.4 (13) Å³	Block, red
Z = 2	0.30 × 0.20 × 0.15 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2871 independent reflections
Radiation source: fine-focus sealed tube	2586 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −8→4
T_min = 0.807, T_max = 0.875	k = −16→15
8060 measured reflections	l = −20→20

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0431P)² + 0.3009P] where P = (F_o² + 2F_c²)/3
2871 reflections	(Δ/σ)_max < 0.001
214 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

(C₁₂H₁₀N₃)₂[Ni(C₄N₂S₂)₂]	V = 1631.4 (13) Å³
M_r = 731.53	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.115 (3) Å	µ = 0.89 mm⁻¹
b = 13.623 (6) Å	T = 298 K
c = 17.186 (8) Å	0.30 × 0.20 × 0.15 mm
β = 101.671 (5)°

Data collection top

Bruker SMART APEX CCD diffractometer	2871 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	2586 reflections with I > 2σ(I)
T_min = 0.807, T_max = 0.875	R_int = 0.020
8060 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.074	H-atom parameters constrained
S = 1.06	Δρ_max = 0.21 e Å⁻³
2871 reflections	Δρ_min = −0.26 e Å⁻³
214 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
Ni1	0.0000	0.0000	0.0000	0.04070 (11)
C1	0.0668 (2)	0.13286 (12)	0.14603 (9)	0.0452 (4)
C2	0.2425 (2)	0.09233 (12)	0.14864 (10)	0.0464 (4)
C3	0.4020 (3)	0.11475 (13)	0.21086 (11)	0.0566 (4)
C4	0.0334 (2)	0.19910 (13)	0.20637 (10)	0.0508 (4)
C5	0.3059 (2)	0.61780 (13)	−0.03334 (11)	0.0515 (4)
C6	0.4014 (3)	0.67295 (15)	−0.08013 (11)	0.0608 (5)
H6A	0.3440	0.6865	−0.1326	0.073*
C7	0.5826 (3)	0.70790 (15)	−0.04870 (11)	0.0594 (5)
H7A	0.6473	0.7448	−0.0805	0.071*
C8	0.6697 (2)	0.68900 (12)	0.02927 (10)	0.0473 (4)
C9	0.5730 (2)	0.63300 (13)	0.07578 (10)	0.0513 (4)
H9A	0.6311	0.6190	0.1281	0.062*
C10	0.3910 (3)	0.59771 (13)	0.04520 (11)	0.0550 (4)
H10A	0.3260	0.5608	0.0769	0.066*
C11	0.1164 (3)	0.58128 (16)	−0.06742 (13)	0.0670 (5)
C12	0.8708 (2)	0.72452 (14)	0.06029 (11)	0.0541 (4)
H12A	0.9486	0.6693	0.0833	0.065*
H12B	0.9232	0.7484	0.0159	0.065*
C13	0.7384 (3)	0.85735 (13)	0.13272 (12)	0.0558 (4)
H13A	0.6171	0.8476	0.1014	0.067*
C14	0.7677 (3)	0.92685 (15)	0.19170 (13)	0.0672 (5)
H14A	0.6632	0.9643	0.1989	0.081*
C15	1.0821 (3)	0.89226 (14)	0.22341 (12)	0.0658 (5)
H15A	1.2038	0.9037	0.2539	0.079*
C16	1.0618 (3)	0.82300 (14)	0.16465 (11)	0.0573 (5)
H16A	1.1684	0.7893	0.1549	0.069*
N1	0.0083 (2)	0.25233 (14)	0.25432 (10)	0.0707 (5)
N2	0.5329 (3)	0.13221 (16)	0.25944 (11)	0.0842 (6)
N3	−0.0327 (3)	0.55373 (19)	−0.09570 (13)	0.0963 (7)
N4	0.88726 (18)	0.80422 (10)	0.12132 (8)	0.0455 (3)
N5	0.9357 (3)	0.94368 (12)	0.23882 (10)	0.0677 (4)
S1	−0.12375 (6)	0.10653 (3)	0.06901 (3)	0.05089 (13)
S2	0.28315 (7)	0.01308 (3)	0.07488 (3)	0.05495 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.04532 (18)	0.03877 (17)	0.03648 (17)	−0.00199 (11)	0.00463 (12)	−0.00037 (10)
C1	0.0529 (9)	0.0417 (8)	0.0406 (8)	−0.0064 (7)	0.0085 (7)	−0.0019 (7)
C2	0.0511 (9)	0.0440 (8)	0.0423 (8)	−0.0041 (7)	0.0051 (7)	−0.0038 (7)
C3	0.0564 (11)	0.0559 (10)	0.0541 (10)	0.0060 (8)	0.0036 (9)	−0.0140 (8)
C4	0.0470 (9)	0.0544 (10)	0.0508 (9)	−0.0046 (7)	0.0094 (8)	−0.0047 (8)
C5	0.0449 (9)	0.0502 (9)	0.0585 (10)	0.0017 (7)	0.0079 (8)	−0.0081 (8)
C6	0.0608 (11)	0.0711 (12)	0.0473 (10)	0.0045 (9)	0.0033 (8)	0.0033 (9)
C7	0.0599 (11)	0.0661 (11)	0.0531 (10)	−0.0045 (9)	0.0135 (8)	0.0121 (9)
C8	0.0461 (9)	0.0454 (9)	0.0512 (9)	−0.0015 (7)	0.0118 (7)	0.0002 (7)
C9	0.0520 (10)	0.0547 (10)	0.0463 (9)	−0.0037 (8)	0.0074 (7)	0.0036 (7)
C10	0.0533 (10)	0.0555 (10)	0.0577 (10)	−0.0076 (8)	0.0147 (8)	0.0039 (8)
C11	0.0542 (12)	0.0750 (13)	0.0690 (13)	−0.0025 (10)	0.0059 (10)	−0.0086 (10)
C12	0.0479 (9)	0.0575 (10)	0.0587 (10)	−0.0046 (8)	0.0153 (8)	−0.0027 (8)
C13	0.0464 (9)	0.0524 (10)	0.0664 (11)	−0.0008 (8)	0.0066 (8)	0.0011 (8)
C14	0.0634 (12)	0.0577 (11)	0.0791 (14)	0.0017 (9)	0.0111 (10)	−0.0062 (10)
C15	0.0651 (12)	0.0559 (11)	0.0669 (12)	−0.0098 (9)	−0.0091 (10)	0.0106 (9)
C16	0.0455 (9)	0.0546 (10)	0.0673 (11)	−0.0028 (8)	0.0006 (8)	0.0099 (9)
N1	0.0665 (11)	0.0800 (12)	0.0676 (11)	0.0002 (9)	0.0182 (8)	−0.0250 (9)
N2	0.0671 (11)	0.0967 (14)	0.0773 (12)	0.0143 (10)	−0.0129 (10)	−0.0363 (11)
N3	0.0612 (12)	0.1261 (19)	0.0940 (15)	−0.0216 (12)	−0.0021 (11)	−0.0063 (14)
N4	0.0427 (7)	0.0434 (7)	0.0499 (8)	−0.0049 (6)	0.0080 (6)	0.0103 (6)
N5	0.0823 (12)	0.0551 (9)	0.0618 (10)	−0.0071 (9)	0.0051 (9)	0.0015 (8)
S1	0.0477 (2)	0.0538 (3)	0.0488 (2)	0.00206 (18)	0.00416 (18)	−0.00887 (18)
S2	0.0479 (3)	0.0615 (3)	0.0517 (3)	0.00499 (19)	0.0009 (2)	−0.01617 (19)

Geometric parameters (Å, º) top

Ni1—S2	2.1674 (9)	C8—C12	1.502 (2)
Ni1—S2ⁱ	2.1674 (9)	C9—C10	1.382 (2)
Ni1—S1	2.1704 (7)	C9—H9A	0.9300
Ni1—S1ⁱ	2.1704 (7)	C10—H10A	0.9300
C1—C2	1.359 (2)	C11—N3	1.138 (3)
C1—C4	1.430 (2)	C12—N4	1.498 (2)
C1—S1	1.7302 (17)	C12—H12A	0.9700
C2—C3	1.426 (2)	C12—H12B	0.9700
C2—S2	1.7334 (18)	C13—N4	1.330 (2)
C3—N2	1.143 (2)	C13—C14	1.372 (3)
C4—N1	1.139 (2)	C13—H13A	0.9300
C5—C6	1.376 (3)	C14—N5	1.322 (3)
C5—C10	1.390 (3)	C14—H14A	0.9300
C5—C11	1.445 (3)	C15—N5	1.325 (3)
C6—C7	1.378 (3)	C15—C16	1.368 (3)
C6—H6A	0.9300	C15—H15A	0.9300
C7—C8	1.382 (2)	C16—N4	1.337 (2)
C7—H7A	0.9300	C16—H16A	0.9300
C8—C9	1.384 (2)

S2—Ni1—S2ⁱ	180.00 (2)	C9—C10—C5	119.44 (17)
S2—Ni1—S1	92.96 (3)	C9—C10—H10A	120.3
S2ⁱ—Ni1—S1	87.04 (3)	C5—C10—H10A	120.3
S2—Ni1—S1ⁱ	87.04 (3)	N3—C11—C5	178.5 (3)
S2ⁱ—Ni1—S1ⁱ	92.96 (3)	N4—C12—C8	114.59 (14)
S1—Ni1—S1ⁱ	180.00 (2)	N4—C12—H12A	108.6
C2—C1—C4	121.29 (15)	C8—C12—H12A	108.6
C2—C1—S1	120.95 (13)	N4—C12—H12B	108.6
C4—C1—S1	117.76 (13)	C8—C12—H12B	108.6
C1—C2—C3	121.67 (15)	H12A—C12—H12B	107.6
C1—C2—S2	121.17 (12)	N4—C13—C14	118.57 (17)
C3—C2—S2	117.14 (13)	N4—C13—H13A	120.7
N2—C3—C2	178.3 (2)	C14—C13—H13A	120.7
N1—C4—C1	179.3 (2)	N5—C14—C13	123.76 (19)
C6—C5—C10	120.33 (16)	N5—C14—H14A	118.1
C6—C5—C11	118.78 (17)	C13—C14—H14A	118.1
C10—C5—C11	120.88 (17)	N5—C15—C16	122.83 (19)
C5—C6—C7	119.54 (17)	N5—C15—H15A	118.6
C5—C6—H6A	120.2	C16—C15—H15A	118.6
C7—C6—H6A	120.2	N4—C16—C15	119.37 (18)
C6—C7—C8	121.07 (17)	N4—C16—H16A	120.3
C6—C7—H7A	119.5	C15—C16—H16A	120.3
C8—C7—H7A	119.5	C13—N4—C16	119.44 (16)
C7—C8—C9	119.00 (16)	C13—N4—C12	123.08 (14)
C7—C8—C12	119.48 (16)	C16—N4—C12	117.47 (15)
C9—C8—C12	121.42 (16)	C14—N5—C15	115.85 (18)
C10—C9—C8	120.61 (16)	C1—S1—Ni1	102.41 (7)
C10—C9—H9A	119.7	C2—S2—Ni1	102.28 (6)
C8—C9—H9A	119.7

Symmetry code: (i) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	(C₁₂H₁₀N₃)₂[Ni(C₄N₂S₂)₂]
M_r	731.53
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	7.115 (3), 13.623 (6), 17.186 (8)
β (°)	101.671 (5)
V (Å³)	1631.4 (13)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.89
Crystal size (mm)	0.30 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2002)
T_min, T_max	0.807, 0.875
No. of measured, independent and observed [I > 2σ(I)] reflections	8060, 2871, 2586
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.074, 1.06
No. of reflections	2871
No. of parameters	214
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.26

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank the Science and Technology Department of Jiangsu Province, China (grant No. BK2007184).

References

Bigoli, F., Deplano, P., Mercuri, M. L., Pellinghelli, M. A., Pilia, L., Pintus, G., Serpe, A. & Trogu, E. F. (2002). Inorg. Chem. 41, 5241–5248. Web of Science CSD CrossRef PubMed CAS Google Scholar
Davison, A. & Holm, H. R. (1967). Inorg. Synth. 10, 8–26. CrossRef CAS Google Scholar
Duan, H.-B., Ren, X.-M. & Meng, Q.-J. (2010). Coord. Chem. Rev. 254, 1509–1522. Web of Science CrossRef CAS Google Scholar
Pei, W.-B., Wu, J.-S., Tian, Z.-F., Ren, X.-M. & Song, Y. (2011). Inorg. Chem. 50, 3970–3980. Web of Science CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2002). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.