Bis[1-(2,6-dichloro­benz­yl)-3-methyl­pyrazin-1-ium] bis­(maleonitrile­dithiol­ato)nickelate(II)

In the crystal structure of the title compound, (C₁₂H₁₁Cl₂N₂)₂[Ni(C₄N₂S₂)₂], the Ni^II complex dianion is located on an inversion centre. The Ni^II atom is coordinated by four S atoms in a square-planar geometry. In the cation, the dihedral angle between the benzene and pyrazine rings is 85.2 (2)°.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.055
• wR factor = 0.114
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   298.000
            Value of melting point given =     0.000
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C1     -   C2     ...       1.44 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C3     -   C4     ...       1.44 Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C7     --  C8      ..       0.12  Ang.
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C16

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Molecular solids based on transition metal dithiolene complexes have attracted intense interest in recent years, not only owing to the fundamental research of magnetic interactions and magneto-structural correlations but also to the development of new functional molecule-based materials (Robertson & Cronin, 2002). Much work has been performed in molecular solids based on M[dithiolene]₂ complexes owing to their application as building blocks in molecular-based materials showing magnetic, superconducting and optical properties (Nishijo et al., 2000; Ni et al., 2005). Herein, we report the crystal structure of the title compound, (I).

The molecular structure of (I) is illustrated in Fig. 1. Compound (I) crystallizes in monoclinic system, with one half [Ni(mnt)₂]^2- dianion and one 1-(2,6-dichlorobenzyl)-3-methylpyrazine cation in an asymmetric unit. The anion [Ni(mnt)₂]^2- possesses an approximated planar geometry and most of the bond lengths and angles are in good agreement with the various [Ni(mnt)₂]^2- compounds (Ni et al., 2004; Ren et al., 2004).

Related literature

For general background, see: Ni et al. (2005); Nishijo et al. (2000); Robertson & Cronin (2002). For related structures, see: Ni et al. (2004); Ren et al. (2004).

S2. Experimental

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-(2,6-dichlorobenzyl)-3-methylpyrazine iodide (952 mg, 2.5 mmol) in methanol (10 mL) was added to the mixture. The black precipitate that was immediately formed was filtered off and washed with methanol. The crude product was recrystallized in acetone (20 mL) to give black block crystals. Anal. Calcd. for C₃₂H₂₂Cl₄N₈NiS₄: C 48.73, H 2.81, N 14.21%. Found: C 48.69, H 2.78, N 14.09%.

S3. Refinement

The H atoms were placed in geometrically idealized positions (C—H = 0.93–0.97 Å) and refined as riding atoms, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level. The suffix A corresponds to symmetry code (-x, -y+1, -z).

Bis[1-(2,6-dichlorobenzyl)-3-methylpyrazin-1-ium] bis(maleonitriledithiolato)nickelate(II)

Crystal data

(C12H11Cl2N2)2[Ni(C4N2S2)2]	F(000) = 860
Mr = 847.33	Dx = 1.566 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 773 reflections
a = 9.081 (2) Å	θ = 2.6–21.2°
b = 20.238 (5) Å	µ = 1.11 mm^−1
c = 10.489 (2) Å	T = 298 K
β = 111.243 (4)°	Block, black
V = 1796.6 (7) Å^3	0.30 × 0.20 × 0.20 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	3159 independent reflections
Radiation source: fine-focus sealed tube	2170 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.086
ϕ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→6
Tmin = 0.732, Tmax = 0.809	k = −24→23
8822 measured reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0362P)^2] where P = (Fo^2 + 2Fc^2)/3
3159 reflections	(Δ/σ)max = 0.001
224 parameters	Δρmax = 0.51 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.0000	0.5000	0.0000	0.0410 (2)
C1	0.1965 (5)	0.45625 (18)	−0.1702 (4)	0.0434 (10)
C2	0.3109 (6)	0.45822 (19)	−0.2353 (5)	0.0475 (11)
C3	−0.0857 (5)	0.59184 (19)	0.1944 (4)	0.0445 (11)
C4	−0.0777 (5)	0.6476 (2)	0.2820 (5)	0.0489 (11)
C5	0.5497 (5)	0.67689 (19)	0.7483 (4)	0.0418 (10)
C6	0.4392 (5)	0.6850 (2)	0.6168 (5)	0.0508 (11)
C7	0.3690 (6)	0.7445 (3)	0.5682 (5)	0.0676 (14)
H7	0.2936	0.7477	0.4804	0.081*
C8	0.4110 (6)	0.7986 (2)	0.6501 (6)	0.0735 (16)
H8	0.3661	0.8394	0.6172	0.088*
C9	0.5185 (6)	0.7936 (2)	0.7801 (6)	0.0675 (14)
H9	0.5465	0.8309	0.8356	0.081*
C10	0.5857 (5)	0.7331 (2)	0.8293 (5)	0.0505 (12)
C11	0.6274 (5)	0.61171 (19)	0.7983 (4)	0.0486 (11)
H11A	0.6794	0.6130	0.8970	0.058*
H11B	0.5479	0.5772	0.7759	0.058*
C12	0.7394 (5)	0.53854 (19)	0.6677 (5)	0.0512 (12)
H12	0.6629	0.5071	0.6629	0.061*
C13	0.8486 (6)	0.5274 (2)	0.6073 (4)	0.0524 (12)
H13	0.8429	0.4881	0.5597	0.063*
C14	0.9720 (5)	0.6256 (2)	0.6865 (4)	0.0448 (10)
C15	0.8622 (5)	0.63866 (18)	0.7459 (4)	0.0408 (10)
H15	0.8696	0.6776	0.7949	0.049*
C16	1.1035 (5)	0.6723 (2)	0.7000 (5)	0.0666 (14)
H16A	1.2027	0.6502	0.7430	0.100*
H16B	1.0971	0.7094	0.7547	0.100*
H16C	1.0953	0.6874	0.6109	0.100*
Cl1	0.38504 (16)	0.61665 (7)	0.50983 (14)	0.0775 (4)
Cl2	0.71852 (16)	0.72925 (6)	0.99706 (13)	0.0719 (4)
N1	0.4021 (5)	0.46159 (18)	−0.2871 (4)	0.0651 (12)
N2	−0.0664 (5)	0.69443 (19)	0.3446 (4)	0.0688 (12)
N3	0.7460 (4)	0.59632 (15)	0.7340 (3)	0.0415 (9)
N4	0.9619 (4)	0.57012 (18)	0.6139 (4)	0.0535 (10)
S1	0.20391 (14)	0.51963 (5)	−0.05585 (12)	0.0484 (3)
S2	0.05266 (14)	0.59091 (5)	0.11563 (12)	0.0532 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0481 (5)	0.0298 (4)	0.0442 (5)	0.0004 (3)	0.0155 (4)	−0.0004 (3)
C1	0.053 (3)	0.030 (2)	0.048 (3)	0.002 (2)	0.018 (2)	0.0027 (18)
C2	0.058 (3)	0.031 (2)	0.054 (3)	−0.002 (2)	0.021 (3)	0.000 (2)
C3	0.054 (3)	0.034 (2)	0.047 (3)	0.005 (2)	0.020 (2)	−0.0004 (19)
C4	0.056 (3)	0.037 (3)	0.056 (3)	0.001 (2)	0.024 (2)	0.002 (2)
C5	0.040 (3)	0.036 (2)	0.057 (3)	−0.0008 (18)	0.027 (2)	0.006 (2)
C6	0.042 (3)	0.050 (3)	0.066 (3)	−0.005 (2)	0.027 (2)	0.005 (2)
C7	0.049 (3)	0.075 (4)	0.077 (4)	0.015 (3)	0.021 (3)	0.031 (3)
C8	0.075 (4)	0.045 (3)	0.113 (5)	0.025 (3)	0.049 (4)	0.021 (3)
C9	0.079 (4)	0.044 (3)	0.098 (4)	0.008 (3)	0.053 (3)	0.001 (3)
C10	0.051 (3)	0.045 (3)	0.066 (3)	0.005 (2)	0.034 (2)	0.005 (2)
C11	0.055 (3)	0.043 (2)	0.057 (3)	−0.001 (2)	0.031 (2)	0.005 (2)
C12	0.052 (3)	0.033 (2)	0.066 (3)	0.000 (2)	0.019 (2)	0.003 (2)
C13	0.059 (3)	0.041 (3)	0.054 (3)	0.005 (2)	0.016 (2)	−0.004 (2)
C14	0.042 (3)	0.046 (3)	0.046 (3)	0.001 (2)	0.015 (2)	0.003 (2)
C15	0.044 (3)	0.029 (2)	0.047 (3)	−0.0017 (19)	0.014 (2)	0.0026 (18)
C16	0.056 (3)	0.059 (3)	0.089 (4)	−0.011 (2)	0.032 (3)	−0.007 (3)
Cl1	0.0753 (10)	0.0753 (9)	0.0747 (10)	−0.0217 (7)	0.0185 (7)	−0.0094 (7)
Cl2	0.0806 (10)	0.0729 (9)	0.0635 (9)	−0.0026 (7)	0.0276 (7)	−0.0100 (6)
N1	0.070 (3)	0.052 (3)	0.083 (3)	−0.004 (2)	0.040 (3)	−0.001 (2)
N2	0.091 (3)	0.045 (2)	0.076 (3)	−0.004 (2)	0.036 (2)	−0.017 (2)
N3	0.046 (2)	0.0282 (19)	0.049 (2)	0.0030 (15)	0.0164 (17)	0.0058 (15)
N4	0.053 (3)	0.054 (2)	0.053 (2)	0.0067 (19)	0.0196 (19)	−0.0017 (19)
S1	0.0551 (8)	0.0365 (6)	0.0549 (8)	−0.0057 (5)	0.0214 (6)	−0.0049 (5)
S2	0.0621 (8)	0.0388 (6)	0.0658 (8)	−0.0115 (5)	0.0316 (6)	−0.0107 (5)

Geometric parameters (Å, º)

Ni1—S2	2.1596 (11)	C8—H8	0.9300
Ni1—S2^i	2.1596 (11)	C9—C10	1.382 (6)
Ni1—S1^i	2.1715 (12)	C9—H9	0.9300
Ni1—S1	2.1715 (12)	C10—Cl2	1.737 (5)
C1—C3^i	1.356 (5)	C11—N3	1.496 (5)
C1—C2	1.436 (6)	C11—H11A	0.9700
C1—S1	1.741 (4)	C11—H11B	0.9700
C2—N1	1.145 (5)	C12—N3	1.351 (5)
C3—C1^i	1.356 (5)	C12—C13	1.375 (6)
C3—C4	1.441 (6)	C12—H12	0.9300
C3—S2	1.736 (4)	C13—N4	1.326 (5)
C4—N2	1.136 (5)	C13—H13	0.9300
C5—C10	1.387 (5)	C14—N4	1.341 (5)
C5—C6	1.391 (6)	C14—C15	1.379 (5)
C5—C11	1.498 (5)	C14—C16	1.489 (6)
C6—C7	1.370 (6)	C15—N3	1.330 (5)
C6—Cl1	1.737 (4)	C15—H15	0.9300
C7—C8	1.358 (7)	C16—H16A	0.9600
C7—H7	0.9300	C16—H16B	0.9600
C8—C9	1.363 (7)	C16—H16C	0.9600
S2—Ni1—S2^i	180.00 (3)	C5—C10—Cl2	120.4 (3)
S2—Ni1—S1^i	92.37 (4)	N3—C11—C5	110.5 (3)
S2^i—Ni1—S1^i	87.63 (4)	N3—C11—H11A	109.6
S2—Ni1—S1	87.63 (4)	C5—C11—H11A	109.6
S2^i—Ni1—S1	92.37 (4)	N3—C11—H11B	109.6
S1^i—Ni1—S1	180.0	C5—C11—H11B	109.6
C3^i—C1—C2	123.1 (4)	H11A—C11—H11B	108.1
C3^i—C1—S1	119.9 (3)	N3—C12—C13	118.3 (4)
C2—C1—S1	117.0 (3)	N3—C12—H12	120.8
N1—C2—C1	178.2 (4)	C13—C12—H12	120.8
C1^i—C3—C4	123.0 (4)	N4—C13—C12	122.9 (4)
C1^i—C3—S2	121.3 (3)	N4—C13—H13	118.5
C4—C3—S2	115.7 (3)	C12—C13—H13	118.5
N2—C4—C3	174.5 (5)	N4—C14—C15	120.4 (4)
C10—C5—C6	115.8 (4)	N4—C14—C16	118.2 (4)
C10—C5—C11	122.1 (4)	C15—C14—C16	121.4 (4)
C6—C5—C11	122.1 (4)	N3—C15—C14	120.9 (4)
C7—C6—C5	123.0 (4)	N3—C15—H15	119.6
C7—C6—Cl1	118.3 (4)	C14—C15—H15	119.6
C5—C6—Cl1	118.7 (3)	C14—C16—H16A	109.5
C8—C7—C6	119.1 (5)	C14—C16—H16B	109.5
C8—C7—H7	120.5	H16A—C16—H16B	109.5
C6—C7—H7	120.5	C14—C16—H16C	109.5
C7—C8—C9	120.6 (5)	H16A—C16—H16C	109.5
C7—C8—H8	119.7	H16B—C16—H16C	109.5
C9—C8—H8	119.7	C15—N3—C12	119.4 (4)
C8—C9—C10	119.9 (5)	C15—N3—C11	120.0 (3)
C8—C9—H9	120.0	C12—N3—C11	120.5 (3)
C10—C9—H9	120.0	C13—N4—C14	117.9 (4)
C9—C10—C5	121.6 (4)	C1—S1—Ni1	103.14 (15)
C9—C10—Cl2	118.0 (4)	C3—S2—Ni1	103.02 (14)
C10—C5—C6—C7	0.1 (6)	C16—C14—C15—N3	−179.5 (4)
C11—C5—C6—C7	−178.7 (4)	C14—C15—N3—C12	2.8 (6)
C10—C5—C6—Cl1	−178.9 (3)	C14—C15—N3—C11	−179.5 (4)
C11—C5—C6—Cl1	2.3 (5)	C13—C12—N3—C15	−3.9 (6)
C5—C6—C7—C8	1.6 (7)	C13—C12—N3—C11	178.4 (4)
Cl1—C6—C7—C8	−179.4 (4)	C5—C11—N3—C15	56.1 (5)
C6—C7—C8—C9	−1.7 (8)	C5—C11—N3—C12	−126.2 (4)
C7—C8—C9—C10	0.1 (8)	C12—C13—N4—C14	2.1 (6)
C8—C9—C10—C5	1.7 (7)	C15—C14—N4—C13	−3.3 (6)
C8—C9—C10—Cl2	−178.5 (4)	C16—C14—N4—C13	177.1 (4)
C6—C5—C10—C9	−1.7 (6)	C3^i—C1—S1—Ni1	−4.5 (4)
C11—C5—C10—C9	177.1 (4)	C2—C1—S1—Ni1	175.2 (3)
C6—C5—C10—Cl2	178.5 (3)	S2—Ni1—S1—C1	−175.14 (14)
C11—C5—C10—Cl2	−2.7 (5)	S2^i—Ni1—S1—C1	4.86 (14)
C10—C5—C11—N3	−105.5 (4)	C1^i—C3—S2—Ni1	−2.9 (4)
C6—C5—C11—N3	73.2 (5)	C4—C3—S2—Ni1	179.2 (3)
N3—C12—C13—N4	1.5 (6)	S1^i—Ni1—S2—C3	4.39 (15)
N4—C14—C15—N3	0.9 (6)	S1—Ni1—S2—C3	−175.61 (15)

Symmetry code: (i) −x, −y+1, −z.