Acta Cryst. (2009). E65, m599 [ doi:10.1107/S1600536809015360 ]
In the title complex, (C12H10FN2)2[Ni(C4N2S2)2], the anion lies on an inversion center with the NiII ion coordinated by four S atoms in a slightly distorted square-planar environment. In the unique cation, the dihedral angle between the benzene and pyridine rings is 7.1 (2) Å.
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. A solution of o-fluorbenzylidene-1-aminopyridinium bromide(665 mg, 2.5 mmol) in methanol (10 mL) was added to the mixture, and the red precipitate that was immediately formed was filtered off, and washed with methanol. The crude product was recrystallized in acetone (20 mL) to give red block crystals. Anal. Calcd. for C32 H20 F2 N8 Ni S4: C, 51.83; H, 2.72; N, 15.11%. Found: C, 51.96; H, 2.93; N, 15.03%.
The H atoms were placed in geometrically idealized positions (C—H = 0.93 Å) and refined as riding atoms, with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./lh2806fig1thm.gif)
| Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level. Only the symmetry unique anion is shown. Symmetry code (A): -x, -y+1, -z. |
| (C12H10FN2)2[Ni(C4N2S2)2] | V = 788.4 (2) Å3 |
| Mr = 741.51 | Z = 1 |
| Triclinic, P1 | F(000) = 378 |
| Hall symbol: -P 1 | Dx = 1.562 Mg m−3 |
| a = 7.9248 (13) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 9.1774 (15) Å | θ = 1.9–26.0° |
| c = 11.1526 (18) Å | µ = 0.93 mm−1 |
| α = 88.326 (3)° | T = 293 K |
| β = 77.202 (4)° | Block, red |
| γ = 85.448 (4)° | 0.30 × 0.20 × 0.20 mm |
| Bruker SMART CCD area-detector diffractometer | 3030 independent reflections |
| Radiation source: fine-focus sealed tube | 1785 reflections with I > 2σ(I) |
| graphite | Rint = 0.038 |
| φ and ω scans | θmax = 26.0°, θmin = 1.9° |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −8→9 |
| Tmin = 0.732, Tmax = 0.809 | k = −11→11 |
| 4282 measured reflections | l = −13→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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.094 | H-atom parameters constrained |
| S = 0.76 | w = 1/[σ2(Fo2) + (0.0323P)2] where P = (Fo2 + 2Fc2)/3 |
| 3030 reflections | (Δ/σ)max = 0.004 |
| 214 parameters | Δρmax = 0.31 e Å−3 |
| 0 restraints | Δρmin = −0.24 e Å−3 |
| (C12H10FN2)2[Ni(C4N2S2)2] | γ = 85.448 (4)° |
| Mr = 741.51 | V = 788.4 (2) Å3 |
| Triclinic, P1 | Z = 1 |
| a = 7.9248 (13) Å | Mo Kα radiation |
| b = 9.1774 (15) Å | µ = 0.93 mm−1 |
| c = 11.1526 (18) Å | T = 293 K |
| α = 88.326 (3)° | 0.30 × 0.20 × 0.20 mm |
| β = 77.202 (4)° |
| Bruker SMART CCD area-detector diffractometer | 3030 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1785 reflections with I > 2σ(I) |
| Tmin = 0.732, Tmax = 0.809 | Rint = 0.038 |
| 4282 measured reflections | θmax = 26.0° |
| R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
| wR(F2) = 0.094 | Δρmax = 0.31 e Å−3 |
| S = 0.76 | Δρmin = −0.24 e Å−3 |
| 3030 reflections | Absolute structure: ? |
| 214 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | ||
| F1 | 0.5021 (3) | 0.3555 (2) | −0.1896 (2) | 0.0724 (7) | |
| N7 | 0.7362 (4) | 0.1871 (3) | 0.1593 (3) | 0.0528 (8) | |
| N8 | 0.7118 (5) | 0.1192 (3) | 0.0532 (3) | 0.0646 (10) | |
| C21 | 0.5600 (5) | 0.2153 (4) | −0.2199 (4) | 0.0561 (11) | |
| C22 | 0.5388 (6) | 0.1628 (5) | −0.3283 (4) | 0.0735 (13) | |
| H22A | 0.4832 | 0.2200 | −0.3804 | 0.088* | |
| C23 | 0.6029 (6) | 0.0220 (5) | −0.3571 (4) | 0.0797 (14) | |
| H23A | 0.5949 | −0.0156 | −0.4320 | 0.096* | |
| C24 | 0.6779 (6) | −0.0643 (5) | −0.2792 (4) | 0.0742 (14) | |
| H24A | 0.7179 | −0.1602 | −0.3001 | 0.089* | |
| C25 | 0.6944 (5) | −0.0094 (4) | −0.1700 (4) | 0.0609 (11) | |
| H25A | 0.7452 | −0.0686 | −0.1166 | 0.073* | |
| C26 | 0.6362 (5) | 0.1333 (4) | −0.1381 (3) | 0.0484 (10) | |
| C27 | 0.6580 (5) | 0.1978 (4) | −0.0257 (4) | 0.0531 (10) | |
| H27A | 0.6319 | 0.2974 | −0.0126 | 0.064* | |
| C28 | 0.8296 (6) | 0.1020 (4) | 0.2236 (4) | 0.0616 (12) | |
| H28A | 0.8723 | 0.0089 | 0.1956 | 0.074* | |
| C29 | 0.8626 (6) | 0.1496 (4) | 0.3287 (4) | 0.0704 (13) | |
| H29A | 0.9291 | 0.0905 | 0.3725 | 0.085* | |
| C30 | 0.7965 (5) | 0.2868 (4) | 0.3703 (4) | 0.0622 (12) | |
| H30A | 0.8182 | 0.3215 | 0.4425 | 0.075* | |
| C31 | 0.6997 (6) | 0.3708 (4) | 0.3049 (4) | 0.0667 (13) | |
| H31A | 0.6533 | 0.4632 | 0.3326 | 0.080* | |
| C32 | 0.6708 (6) | 0.3200 (4) | 0.1996 (4) | 0.0700 (13) | |
| H32A | 0.6048 | 0.3780 | 0.1546 | 0.084* | |
| Ni1 | 0.0000 | 0.5000 | 0.0000 | 0.0484 (2) | |
| S1 | 0.17387 (15) | 0.40603 (10) | 0.11191 (9) | 0.0589 (3) | |
| S2 | −0.08272 (14) | 0.68427 (10) | 0.12200 (9) | 0.0585 (3) | |
| N1 | 0.2744 (5) | 0.4501 (4) | 0.4175 (3) | 0.0771 (12) | |
| N2 | −0.0466 (5) | 0.8166 (4) | 0.4231 (3) | 0.0776 (12) | |
| C1 | −0.0194 (5) | 0.7374 (4) | 0.3440 (4) | 0.0571 (11) | |
| C2 | 0.0169 (5) | 0.6389 (4) | 0.2423 (3) | 0.0490 (10) | |
| C3 | 0.1256 (5) | 0.5188 (4) | 0.2397 (3) | 0.0501 (10) | |
| C4 | 0.2087 (6) | 0.4806 (4) | 0.3384 (4) | 0.0553 (11) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| F1 | 0.0756 (18) | 0.0615 (15) | 0.0818 (18) | 0.0122 (13) | −0.0271 (14) | −0.0013 (13) |
| N7 | 0.063 (2) | 0.0415 (18) | 0.054 (2) | 0.0031 (17) | −0.0156 (18) | −0.0038 (16) |
| N8 | 0.088 (3) | 0.050 (2) | 0.062 (2) | 0.0107 (19) | −0.033 (2) | −0.0115 (18) |
| C21 | 0.049 (3) | 0.057 (3) | 0.061 (3) | −0.001 (2) | −0.010 (2) | −0.006 (2) |
| C22 | 0.076 (4) | 0.084 (3) | 0.067 (3) | −0.005 (3) | −0.031 (3) | 0.004 (3) |
| C23 | 0.089 (4) | 0.091 (4) | 0.066 (3) | −0.004 (3) | −0.027 (3) | −0.023 (3) |
| C24 | 0.090 (4) | 0.062 (3) | 0.072 (3) | 0.006 (3) | −0.022 (3) | −0.021 (3) |
| C25 | 0.070 (3) | 0.049 (2) | 0.068 (3) | 0.003 (2) | −0.026 (2) | −0.006 (2) |
| C26 | 0.048 (3) | 0.050 (2) | 0.048 (2) | −0.006 (2) | −0.010 (2) | −0.0039 (19) |
| C27 | 0.053 (3) | 0.044 (2) | 0.061 (3) | 0.003 (2) | −0.011 (2) | −0.007 (2) |
| C28 | 0.078 (3) | 0.046 (2) | 0.062 (3) | 0.010 (2) | −0.024 (2) | −0.001 (2) |
| C29 | 0.091 (4) | 0.058 (3) | 0.068 (3) | 0.013 (3) | −0.036 (3) | −0.005 (2) |
| C30 | 0.072 (3) | 0.064 (3) | 0.053 (3) | −0.001 (2) | −0.020 (2) | −0.009 (2) |
| C31 | 0.089 (4) | 0.050 (3) | 0.060 (3) | 0.014 (2) | −0.019 (3) | −0.016 (2) |
| C32 | 0.095 (4) | 0.053 (3) | 0.066 (3) | 0.026 (2) | −0.035 (3) | −0.012 (2) |
| Ni1 | 0.0527 (5) | 0.0408 (4) | 0.0520 (5) | 0.0016 (3) | −0.0130 (4) | −0.0090 (3) |
| S1 | 0.0704 (8) | 0.0504 (6) | 0.0575 (7) | 0.0119 (5) | −0.0214 (6) | −0.0151 (5) |
| S2 | 0.0655 (8) | 0.0496 (6) | 0.0631 (7) | 0.0100 (5) | −0.0230 (6) | −0.0163 (5) |
| N1 | 0.100 (3) | 0.068 (2) | 0.068 (3) | 0.008 (2) | −0.032 (2) | −0.010 (2) |
| N2 | 0.109 (3) | 0.061 (2) | 0.066 (3) | 0.007 (2) | −0.028 (2) | −0.0186 (19) |
| C1 | 0.064 (3) | 0.051 (3) | 0.058 (3) | −0.002 (2) | −0.018 (2) | 0.000 (2) |
| C2 | 0.050 (3) | 0.039 (2) | 0.056 (3) | −0.0034 (19) | −0.008 (2) | −0.0112 (19) |
| C3 | 0.057 (3) | 0.043 (2) | 0.051 (3) | 0.000 (2) | −0.013 (2) | −0.0091 (19) |
| C4 | 0.068 (3) | 0.042 (2) | 0.055 (3) | 0.001 (2) | −0.011 (2) | −0.011 (2) |
| F1—C21 | 1.358 (4) | C29—C30 | 1.378 (5) |
| N7—C28 | 1.335 (4) | C29—H29A | 0.9300 |
| N7—C32 | 1.337 (4) | C30—C31 | 1.355 (5) |
| N7—N8 | 1.410 (4) | C30—H30A | 0.9300 |
| N8—C27 | 1.249 (4) | C31—C32 | 1.348 (5) |
| C21—C22 | 1.364 (5) | C31—H31A | 0.9300 |
| C21—C26 | 1.377 (5) | C32—H32A | 0.9300 |
| C22—C23 | 1.371 (5) | Ni1—S2i | 2.1689 (10) |
| C22—H22A | 0.9300 | Ni1—S2 | 2.1689 (9) |
| C23—C24 | 1.360 (5) | Ni1—S1i | 2.1703 (10) |
| C23—H23A | 0.9300 | Ni1—S1 | 2.1703 (10) |
| C24—C25 | 1.369 (4) | S1—C3 | 1.741 (3) |
| C24—H24A | 0.9300 | S2—C2 | 1.726 (4) |
| C25—C26 | 1.382 (5) | N1—C4 | 1.138 (4) |
| C25—H25A | 0.9300 | N2—C1 | 1.132 (4) |
| C26—C27 | 1.451 (4) | C1—C2 | 1.436 (5) |
| C27—H27A | 0.9300 | C2—C3 | 1.341 (5) |
| C28—C29 | 1.348 (5) | C3—C4 | 1.424 (5) |
| C28—H28A | 0.9300 | ||
| C28—N7—C32 | 120.4 (3) | C28—C29—C30 | 119.2 (4) |
| C28—N7—N8 | 113.1 (3) | C28—C29—H29A | 120.4 |
| C32—N7—N8 | 126.4 (3) | C30—C29—H29A | 120.4 |
| C27—N8—N7 | 118.0 (3) | C31—C30—C29 | 119.3 (4) |
| F1—C21—C22 | 118.7 (4) | C31—C30—H30A | 120.3 |
| F1—C21—C26 | 117.7 (3) | C29—C30—H30A | 120.3 |
| C22—C21—C26 | 123.5 (4) | C32—C31—C30 | 119.8 (4) |
| C21—C22—C23 | 117.0 (4) | C32—C31—H31A | 120.1 |
| C21—C22—H22A | 121.5 | C30—C31—H31A | 120.1 |
| C23—C22—H22A | 121.5 | N7—C32—C31 | 120.6 (4) |
| C24—C23—C22 | 121.9 (4) | N7—C32—H32A | 119.7 |
| C24—C23—H23A | 119.1 | C31—C32—H32A | 119.7 |
| C22—C23—H23A | 119.1 | S2i—Ni1—S2 | 180.0 |
| C23—C24—C25 | 119.7 (4) | S2i—Ni1—S1i | 92.10 (4) |
| C23—C24—H24A | 120.1 | S2—Ni1—S1i | 87.90 (4) |
| C25—C24—H24A | 120.1 | S2i—Ni1—S1 | 87.90 (4) |
| C24—C25—C26 | 120.7 (4) | S2—Ni1—S1 | 92.10 (4) |
| C24—C25—H25A | 119.7 | S1i—Ni1—S1 | 180.00 (4) |
| C26—C25—H25A | 119.7 | C3—S1—Ni1 | 102.69 (14) |
| C21—C26—C25 | 117.1 (4) | C2—S2—Ni1 | 102.72 (13) |
| C21—C26—C27 | 120.4 (4) | N2—C1—C2 | 178.9 (5) |
| C25—C26—C27 | 122.5 (4) | C3—C2—C1 | 121.6 (4) |
| N8—C27—C26 | 119.8 (3) | C3—C2—S2 | 121.5 (3) |
| N8—C27—H27A | 120.1 | C1—C2—S2 | 116.9 (3) |
| C26—C27—H27A | 120.1 | C2—C3—C4 | 121.9 (3) |
| N7—C28—C29 | 120.7 (4) | C2—C3—S1 | 120.3 (3) |
| N7—C28—H28A | 119.7 | C4—C3—S1 | 117.7 (3) |
| C29—C28—H28A | 119.7 | N1—C4—C3 | 179.7 (5) |
| Symmetry codes: (i) −x, −y+1, −z. |
The authors thank the Natural Science Foundation of High Learning Institutions of Abhui Province, China, for financial support (grant No. KJ2009B275Z).
Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Ni, C. L., Dang, D. B. & Song, Y. (2004). Chem. Phys. Lett. 396, 353–358.
Ni, Z. P., Ren, X. M. & Ma, J. (2005). J. Am. Chem. Soc. 127, 14330–14338.
Nishijo, J., Ogura, E., Yamaura, J. & Miyazaki, A. (2000). Solid State Commun. 116, 661–664.
Ren, X. M., Okudera, H. & Kremer, R. K. (2004). Inorg. Chem. 43, 2569–2576.
Robertson, N. & Cronin, L. (2002). Coord. Chem. Rev. 227, 93–127.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
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 on 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. The asymmetric unit contains one half [Ni(mnt)2]2- (mnt = maleonitriledithiolato) dianion and one o-fluorbenzylidene-1-aminopyrazine cation, the formula unit being generated by an inversion center. In the [Ni(mnt)2]2- cation the bond lengths and angles are in good agreement with related [Ni(mnt)2]2- compounds (Ni et al., 2004; Ren et al., 2004)