Acta Cryst. (2007). E63, m1932 [ doi:10.1107/S1600536807027377 ]
In the crystal structure of the title complex, (C12H11IN)2[Ni(C4N2S2)2], the [Ni(mnt)2]2- anion (mnt is maleonitriledithiolate) lies on an inversion center and possesses a square-planar geometry. Strong S
I stacking interactions are observed between anions and cations in the crystal structure, with SI separations of 3.3863 (9) Å.
Disodium maleonitriledithiolate (Na2mnt) was prepared following a procedure found in the literature (Davison & Holm, 1967). 1-(4'-iodobenzyl)pyridinium bromide was prepared by reacting 4-iodobenzylchlorine with 1.5 equivalent of pyridine in refluxing acetone for 4 h. The white microcrystalline product formed was filtered, washed with acetone and diethyl ether, and dried in vacuum (yield: ca. 80%). NiCl2·6H2O, Na2mnt and 1-(4'-iodobenzyl)pyridinium bromide (molar ratio 1:2:2) were mixed in water. The red precipitated product, (I), was separated, washed with water and then dissolved in a minimum amount of MeCN. This MeCN solution of (I) was kept at 277 K for 6 days, affording single crystals of (I) suitable for structure analysis. Crystals were separated, washed with Et2O and dried in vacuum (Yield: ca. 70%).
All H atoms were placed in calculated positions and refined using a riding model, with C—H bond lengths constrained to 0.93 (aromatic CH) or 0.97 Å (methylene CH2) and Uiso(H) = 1.2Ueq(parent atom).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.
![[Figure 1]](./bh2107fig1thm.gif)
| Fig. 1. : The structure of complex (I), showing 30% probability displacement ellipsoids with numbering scheme [symmetry code: (A) 1 − x, 1 − y, 1 − z]. |
![[Figure 2]](./bh2107fig2thm.gif)
| Fig. 2. : The S···I stacking interactions between anion and cations [symmetry codes: (i) −0.5 − x, −1/2 + y, 0.5 − z; (ii) 1.5 + x, 1.5 − y, −1/2 + z; (A) 1 − x, 1 − y, 1 − z]. |
| (C12H11IN)2[Ni(C4N2S2)2] | Z = 2 |
| Mr = 931.31 | F000 = 908 |
| Monoclinic, P21/n | Dx = 1.751 Mg m−3 |
| Hall symbol: -P 2yn | Mo Kα radiation λ = 0.71073 Å |
| a = 12.7723 (16) Å | θ = 2.5–25.1º |
| b = 10.4489 (13) Å | µ = 2.57 mm−1 |
| c = 13.7585 (17) Å | T = 293 (2) K |
| β = 105.889 (2)º | Block, red |
| V = 1766.0 (4) Å3 | 0.30 × 0.20 × 0.10 mm |
| Bruker SMART CCD area-detector diffractometer | 4243 independent reflections |
| Radiation source: fine-focus sealed tube | 2438 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.070 |
| T = 293(2) K | θmax = 28.3º |
| φ and ω scans | θmin = 1.9º |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −16→11 |
| Tmin = 0.459, Tmax = 0.776 | k = −13→13 |
| 10837 measured reflections | l = −16→18 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
| wR(F2) = 0.072 | w = 1/[σ2(Fo2) + (0.02P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 0.82 | (Δ/σ)max = 0.002 |
| 4243 reflections | Δρmax = 0.43 e Å−3 |
| 205 parameters | Δρmin = −0.69 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| (C12H11IN)2[Ni(C4N2S2)2] | V = 1766.0 (4) Å3 |
| Mr = 931.31 | Z = 2 |
| Monoclinic, P21/n | Mo Kα |
| a = 12.7723 (16) Å | µ = 2.57 mm−1 |
| b = 10.4489 (13) Å | T = 293 (2) K |
| c = 13.7585 (17) Å | 0.30 × 0.20 × 0.10 mm |
| β = 105.889 (2)º |
| Bruker SMART CCD area-detector diffractometer | 4243 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2438 reflections with I > 2σ(I) |
| Tmin = 0.459, Tmax = 0.776 | Rint = 0.070 |
| 10837 measured reflections |
| R[F2 > 2σ(F2)] = 0.036 | 205 parameters |
| wR(F2) = 0.072 | H-atom parameters constrained |
| S = 0.82 | Δρmax = 0.43 e Å−3 |
| 4243 reflections | Δρmin = −0.69 e Å−3 |
| x | y | z | Uiso*/Ueq | ||
| Ni1 | 0.5000 | 0.5000 | 0.5000 | 0.04272 (15) | |
| S1 | 0.35566 (6) | 0.39970 (8) | 0.51129 (7) | 0.0500 (2) | |
| S2 | 0.39653 (7) | 0.66191 (8) | 0.43750 (7) | 0.0572 (2) | |
| I1 | −0.58920 (2) | 0.84666 (3) | 0.104948 (19) | 0.07120 (12) | |
| N1 | 0.2621 (2) | 0.0847 (3) | 0.5759 (2) | 0.0675 (9) | |
| N2 | 0.4103 (2) | 1.0011 (3) | 0.3686 (2) | 0.0642 (8) | |
| N3 | −0.0135 (2) | 0.7533 (3) | 0.2672 (2) | 0.0531 (7) | |
| C1 | 0.3260 (3) | 0.1552 (3) | 0.5657 (2) | 0.0481 (8) | |
| C2 | 0.4039 (2) | 0.2484 (3) | 0.5530 (2) | 0.0417 (7) | |
| C3 | 0.4463 (3) | 0.9027 (3) | 0.3929 (2) | 0.0473 (8) | |
| C4 | 0.4887 (2) | 0.7777 (3) | 0.4259 (2) | 0.0419 (7) | |
| C5 | −0.0119 (4) | 0.8025 (4) | 0.3575 (3) | 0.0818 (12) | |
| H5A | −0.0656 | 0.7792 | 0.3882 | 0.098* | |
| C6 | 0.0671 (4) | 0.8860 (5) | 0.4047 (3) | 0.0906 (15) | |
| H6A | 0.0679 | 0.9183 | 0.4679 | 0.109* | |
| C7 | 0.1447 (3) | 0.9225 (4) | 0.3605 (3) | 0.0791 (12) | |
| H7A | 0.1991 | 0.9795 | 0.3927 | 0.095* | |
| C8 | 0.1415 (3) | 0.8744 (4) | 0.2686 (3) | 0.0770 (12) | |
| H8A | 0.1933 | 0.8994 | 0.2363 | 0.092* | |
| C9 | 0.0622 (3) | 0.7889 (4) | 0.2229 (3) | 0.0619 (10) | |
| H9A | 0.0612 | 0.7554 | 0.1601 | 0.074* | |
| C10 | −0.0975 (3) | 0.6579 (3) | 0.2174 (3) | 0.0736 (12) | |
| H10A | −0.0902 | 0.5827 | 0.2601 | 0.088* | |
| H10B | −0.0848 | 0.6318 | 0.1539 | 0.088* | |
| C11 | −0.2118 (3) | 0.7089 (3) | 0.1972 (3) | 0.0529 (9) | |
| C12 | −0.2872 (3) | 0.6445 (3) | 0.2336 (3) | 0.0577 (9) | |
| H12A | −0.2661 | 0.5729 | 0.2743 | 0.069* | |
| C13 | −0.3943 (3) | 0.6858 (3) | 0.2098 (3) | 0.0552 (9) | |
| H13A | −0.4447 | 0.6429 | 0.2354 | 0.066* | |
| C14 | −0.4253 (3) | 0.7893 (3) | 0.1491 (2) | 0.0505 (8) | |
| C15 | −0.3494 (3) | 0.8555 (3) | 0.1138 (3) | 0.0631 (10) | |
| H15A | −0.3701 | 0.9279 | 0.0738 | 0.076* | |
| C16 | −0.2438 (3) | 0.8144 (3) | 0.1377 (3) | 0.0623 (10) | |
| H16A | −0.1931 | 0.8586 | 0.1132 | 0.075* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ni1 | 0.0384 (3) | 0.0356 (3) | 0.0544 (3) | −0.0057 (3) | 0.0131 (3) | 0.0053 (3) |
| S1 | 0.0388 (5) | 0.0393 (5) | 0.0727 (6) | −0.0041 (4) | 0.0165 (4) | 0.0090 (4) |
| S2 | 0.0403 (5) | 0.0462 (5) | 0.0845 (6) | −0.0026 (4) | 0.0161 (5) | 0.0166 (5) |
| I1 | 0.05189 (17) | 0.0832 (2) | 0.07392 (19) | 0.00774 (13) | 0.00940 (13) | −0.00856 (14) |
| N1 | 0.062 (2) | 0.0524 (19) | 0.089 (2) | −0.0197 (16) | 0.0215 (17) | 0.0109 (17) |
| N2 | 0.064 (2) | 0.0444 (19) | 0.084 (2) | 0.0034 (16) | 0.0200 (17) | 0.0096 (17) |
| N3 | 0.0456 (17) | 0.0469 (18) | 0.0687 (19) | 0.0032 (14) | 0.0187 (15) | −0.0013 (15) |
| C1 | 0.047 (2) | 0.044 (2) | 0.053 (2) | −0.0009 (16) | 0.0123 (16) | 0.0025 (16) |
| C2 | 0.0430 (19) | 0.0344 (17) | 0.0502 (18) | −0.0099 (14) | 0.0171 (15) | −0.0016 (15) |
| C3 | 0.043 (2) | 0.046 (2) | 0.055 (2) | −0.0091 (17) | 0.0169 (16) | −0.0003 (17) |
| C4 | 0.0444 (19) | 0.0369 (18) | 0.0450 (18) | −0.0046 (15) | 0.0132 (15) | 0.0000 (14) |
| C5 | 0.080 (3) | 0.103 (4) | 0.075 (3) | 0.005 (3) | 0.042 (3) | 0.007 (3) |
| C6 | 0.079 (3) | 0.126 (4) | 0.066 (3) | 0.001 (3) | 0.018 (3) | −0.031 (3) |
| C7 | 0.053 (3) | 0.092 (3) | 0.083 (3) | −0.001 (2) | 0.004 (2) | −0.024 (3) |
| C8 | 0.060 (3) | 0.097 (3) | 0.077 (3) | −0.024 (2) | 0.023 (2) | −0.017 (2) |
| C9 | 0.054 (2) | 0.071 (3) | 0.065 (2) | −0.002 (2) | 0.024 (2) | −0.012 (2) |
| C10 | 0.054 (2) | 0.048 (2) | 0.124 (3) | −0.0009 (18) | 0.033 (2) | −0.013 (2) |
| C11 | 0.050 (2) | 0.041 (2) | 0.071 (2) | −0.0046 (17) | 0.0237 (19) | −0.0133 (18) |
| C12 | 0.059 (2) | 0.043 (2) | 0.075 (2) | −0.0022 (18) | 0.024 (2) | 0.0058 (17) |
| C13 | 0.049 (2) | 0.054 (2) | 0.067 (2) | −0.0093 (18) | 0.0249 (19) | −0.0024 (19) |
| C14 | 0.047 (2) | 0.050 (2) | 0.054 (2) | −0.0006 (17) | 0.0126 (17) | −0.0078 (17) |
| C15 | 0.064 (3) | 0.051 (2) | 0.073 (2) | 0.002 (2) | 0.018 (2) | 0.0115 (19) |
| C16 | 0.065 (3) | 0.052 (2) | 0.081 (3) | −0.0044 (19) | 0.038 (2) | 0.006 (2) |
| Ni1—S1i | 2.1629 (8) | C6—H6A | 0.9300 |
| Ni1—S1 | 2.1629 (8) | C7—C8 | 1.351 (5) |
| Ni1—S2i | 2.1739 (9) | C7—H7A | 0.9300 |
| Ni1—S2 | 2.1739 (9) | C8—C9 | 1.367 (5) |
| S1—C2 | 1.737 (3) | C8—H8A | 0.9300 |
| S2—C4 | 1.725 (3) | C9—H9A | 0.9300 |
| I1—C14 | 2.101 (3) | C10—C11 | 1.507 (4) |
| N1—C1 | 1.136 (4) | C10—H10A | 0.9700 |
| N2—C3 | 1.138 (4) | C10—H10B | 0.9700 |
| N3—C9 | 1.329 (4) | C11—C16 | 1.367 (5) |
| N3—C5 | 1.340 (5) | C11—C12 | 1.377 (4) |
| N3—C10 | 1.487 (4) | C12—C13 | 1.385 (4) |
| C1—C2 | 1.436 (4) | C12—H12A | 0.9300 |
| C2—C4i | 1.351 (4) | C13—C14 | 1.357 (4) |
| C3—C4 | 1.439 (5) | C13—H13A | 0.9300 |
| C4—C2i | 1.351 (4) | C14—C15 | 1.384 (4) |
| C5—C6 | 1.358 (6) | C15—C16 | 1.367 (5) |
| C5—H5A | 0.9300 | C15—H15A | 0.9300 |
| C6—C7 | 1.351 (5) | C16—H16A | 0.9300 |
| S1i—Ni1—S1 | 180.0 | C7—C8—H8A | 119.9 |
| S1i—Ni1—S2i | 88.15 (3) | C9—C8—H8A | 119.9 |
| S1—Ni1—S2i | 91.85 (3) | N3—C9—C8 | 120.9 (3) |
| S1i—Ni1—S2 | 91.85 (3) | N3—C9—H9A | 119.6 |
| S1—Ni1—S2 | 88.15 (3) | C8—C9—H9A | 119.6 |
| S2i—Ni1—S2 | 180.0 | N3—C10—C11 | 112.8 (3) |
| C2—S1—Ni1 | 103.46 (10) | N3—C10—H10A | 109.0 |
| C4—S2—Ni1 | 103.07 (11) | C11—C10—H10A | 109.0 |
| C9—N3—C5 | 119.3 (3) | N3—C10—H10B | 109.0 |
| C9—N3—C10 | 120.0 (3) | C11—C10—H10B | 109.0 |
| C5—N3—C10 | 120.7 (3) | H10A—C10—H10B | 107.8 |
| N1—C1—C2 | 177.8 (4) | C16—C11—C12 | 119.2 (3) |
| C4i—C2—C1 | 122.3 (3) | C16—C11—C10 | 120.8 (3) |
| C4i—C2—S1 | 120.1 (2) | C12—C11—C10 | 119.9 (3) |
| C1—C2—S1 | 117.5 (2) | C11—C12—C13 | 120.4 (3) |
| N2—C3—C4 | 177.7 (3) | C11—C12—H12A | 119.8 |
| C2i—C4—C3 | 121.5 (3) | C13—C12—H12A | 119.8 |
| C2i—C4—S2 | 121.2 (2) | C14—C13—C12 | 119.8 (3) |
| C3—C4—S2 | 117.3 (2) | C14—C13—H13A | 120.1 |
| N3—C5—C6 | 120.7 (4) | C12—C13—H13A | 120.1 |
| N3—C5—H5A | 119.6 | C13—C14—C15 | 120.0 (3) |
| C6—C5—H5A | 119.6 | C13—C14—I1 | 120.4 (3) |
| C7—C6—C5 | 120.4 (4) | C15—C14—I1 | 119.6 (3) |
| C7—C6—H6A | 119.8 | C16—C15—C14 | 119.9 (3) |
| C5—C6—H6A | 119.8 | C16—C15—H15A | 120.0 |
| C8—C7—C6 | 118.6 (4) | C14—C15—H15A | 120.0 |
| C8—C7—H7A | 120.7 | C11—C16—C15 | 120.7 (3) |
| C6—C7—H7A | 120.7 | C11—C16—H16A | 119.6 |
| C7—C8—C9 | 120.1 (4) | C15—C16—H16A | 119.6 |
| Symmetry codes: (i) −x+1, −y+1, −z+1. |
The authors thank the Natural Science Foundation for Outstanding Scholars of Anhui Province in China (project No. 044-J-04011) for financial support.
Bruker (2000). SMART, SAINT, SADABS and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.
Coomber, A. T., Beljonne, D., Friend, R. H., Bredas, J. L., Charlton, A., Robertson, N., Underhill, A. E., Kurmoo, M. & Day, P. (1996). Nature (London), 380, 144–146.
Davison, A. & Holm, R. H. (1967). Inorg. Synth. 10, 8–26.
Gama, V., Henriques, R. T., Bonfait, G., Almeida, M., Meetsma, A., Van Smaalen, S. & De Boer, J. L. (1992). J. Am. Chem. Soc. 114, 1986–1989.
Kawamura, T., Miyazaki, Y. & Sorai, M. (1997). Chem. Phys. Lett. 273, 435–438.
Ren, X. M., Akutagawa, T., Nishihara, S., Nakamura, T., Fujita, W. & Awaga, K. (2005). J. Phys. Chem. B, 109, 16610–16615.
Ren, X., Meng, Q., Song, Y., Lu, C., Hu, C. & Chen, X. (2002). Inorg. Chem. 41, 5686–5692.
Ren, X. M., Nishihara, S., Akutagawa, T., Noro, S., Nakamura, T., Fujita, M. & Awaga, T. (2006). Chem. Phys. Lett. 418, 423–427.
Ren, X. M., Okudera, H., Kremer, R. K., Song, Y., He, C., Meng, Q. J. & Wu, P. H. (2004). Inorg. Chem. 43, 2569–2576.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Xie, J. L., Ren, X. M., Song, Y., Zhang, W. W., Liu, W. L., He, C. & Meng, Q. J. (2002). Chem. Commun. pp. 2346–2347.
Xie, J., Ren, X., He, C., Song, Y., Meng, Q., Kremer, R. K. & Yao, Y. (2003). Chem. Phys. Lett. 369, 41–48.
Some charge transfer salts with their cations and anions packed in segregated stacks exhibit unusual properties in magnetism and conductivity (Gama et al., 1992; Coomber et al., 1996; Kawamura et al., 1997; Ren et al., 2002; Xie et al., 2002, 2003). In our previous studies, benzylpyridinium derivatives were employed as the countercations of [M(mnt)2]− ions (M = Ni3+ or Pt3+; mnt2− = maleonitriledithiolate) to prepare a series of compounds with segregated stacks displaying magnetic transitions (Ren et al., 2002, 2004, 2005, 2006; Xie et al., 2002, 2003).
Although all compounds exhibit similar structural features at room temperature, with the anions stacked in columns, the hysteresis loop in the plot of magnetic susceptibility vs. temperature was only observed in a compound that possesses obvious S···I interactions between anion and cations (Ren et al., 2006). In order to gain more information about the relationship between intermolecular interactions and magnetic properties, we are designing a series of [M(mnt)2]2− and [M(mnt)2]− anions (M = Ni and Pt), and investigate their crystal structures.
In the crystal of (I), the asymmetric unit consists of one cation placed on a general position and one-half [Ni(mnt)2]2− dianion lying on an inversion center (Fig. 1). The anionic moiety possesses a square-planar geometry, and the NiII ion coincides with an inversion center. The Ni—S bond lengths are 2.1629 (8) and 2.1739 (9) Å, and the bond angle within the chelate ring is 91.85 (3)°. The cation adopts a conformation in which the benzene and pyridine rings make dihedral angles of 57.4 (3) and 59.8 (3)° with the reference plane N3/C10/C11, respectively. Benzene ring makes a dihedral angle of 84.95 (11)° with the pyridine ring.
Short contacts between S atoms of anions and I atoms of symmetry related cations are observed (Fig. 2). The S1···I1i separation of 3.3863 (9) Å [symmetry code: (i) −1/2 − x, −1/2 + y, 1/2 − z) is small compared to the sum of van der Waals radii of S (1.80 Å) and I (2.04 Å).