Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101009064/ta1318sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009064/ta1318Isup2.hkl |
CCDC reference: 173342
NiCl2·6H2O, disodium maleonitriledithiolate and 1-(4-nitrobenzyl)-2-methylpyridinium chloride (equivalent molar ratio 1:2:2) were combined in water. The precipitated product was filtered off, washed with water and then dissolved in a little MeCN. Iodine (1 mol equivalent) was added to the solution with stirring at room temperature. Three times the resulting volume of MeOH was then added and the mixture allowed to stand overnight. The microcrystals which formed were filtered off, washed with MeOH and dried in vacuo. Single crystals of (I) suitable for structure analysis were obtained by evaporating an MeCN–n-PrOH (1:1 v/v) mixed solution of (I).
H atoms were placed in geometrically calculated positions (C—H = 0.93 Å) with Ueq(H) = 1.2 Ueq(parent atom).
Recently, considerable interest has been focused on low-dimensional molecular solids with novel magnetic properties, such as spin-Peierls transitions (Brown et al., 1998) and room-temperature spin bistability (Fujita & Awaga, 1999). Our aim is to construct quasi-one-dimensional molecule-based magnetic materials formed by platelike maleonitriledithiolene anionic metal complexes [M(mnt)2]- (M is NiIII, PdIII or PtIII). These types of low-dimensional materials are associated with columnar crystallographic packing. Previous work has shown that the geometry of the counter-cations strongly influences the stacking structure of this type of material. Therefore, it is important to select particular counter-cations in order to obtain columnar crystallographic packing. The ground-state conformations of benzylpyridinium derivatives have been extensively investigated by many techniques, and results to date have indicated that the spatial orientation of the benzene and pyridine rings depends on both the electronic and the steric properties of the substituents on the aryl rings (Bulgarevich et al., 1994). The different conformations available to benzylpyridinium derivatives may lead to differences in the geometry of the cations, sufficient to influence the stacking structures of the complexes in the solid state. As a result, the ion-pair complexes consisting of [M(mnt)2]- anions and benzylpyridinium-derived cations present a unique opportunity for the systematic investigation of the fundamental relationship between the stacking structure in the solid and the substituents on the aryl rings. To test this idea, we prepared a series of complexes by systematically varying the substituents on the aryl rings, and found that it is possible to obtain completely separated anions and cations in columnar stacking structures. Herein, we report the crystal structure of the title compound, (I), which has columnar packing. \sch
In the anion of (I), the Ni atom exhibits square-planar coordination geometry involving four S atoms, and the five-membered nickel-containing rings are slightly puckered (Fig. 1), as has been found in other [M(mnt)2]n- structures (Plumlee et al., 1975). The average S—Ni—S bond angle within the five-membered ring is 92.50 (5)° and the average Ni—S bond distance is 2.1477 (13) Å. Other chemically equivalent but crystallographically non-equivalent bond distances within the anion differ by less than three s.u.'s and compare well with those found in [Ni(mnt)2]- complexes (Brunn et al., 1987). The anion is non-planar and the CN groups bend away from the plane of the four S atoms. The CN group with the largest deviation is C1≡N1, and the deviations from the plane defined by the four S atoms are 0.294 (6) Å for N1 and 0.167 (6) Å for C1. The cation adopts a conformation where the dihedral angle between the benzene ring and the C14/C15/N6 reference plane is 44.5 (4)°, and the pyridine ring is twisted towards the reference plane with a dihedral angle of 72.3 (4)°.
The most prominent general structural features of the complex are the completely segregated stacked columns of [Ni(mnt)2]- anions and 1-(4-nitrobenzyl)-2-methylpyridinium cations, as revealed by the projection along the crystallographic a axis in Fig. 2. Completely segregated stacked columns of [Ni(mnt)2]- anions have been infrequently reported (Hobi et al., 1996). The Ni···Ni distances are alternately 3.847 (1) and 4.281 (1) Å within the [Ni(mnt)2]- column. The nearest Ni···Ni contact between [Ni(mnt)2]- columns is much larger at 10.6 Å, and is larger than the Ni···Ni distance within the [Ni(mnt)2]- column. These results indicate that, compared with intracolumnar interactions, the Ni···Ni magnetic exchange interactions between columns may be neglected. Within the 1-(4-nitrobenzyl)-2-methylbenzylpyridinium cation column, the nitro group of one cation is stacked over the benzene ring of an adjacent cation (Fig. 3). This type of packing structure is often found in nitrobenzene derivatives (Harrowfield et al., 1998). The shorter contacts between adjacent nitro groups and benzene rings are: N5···C9i 3.591 (6), N5···C10i 3.505 (6), N5···C11i 3.636 (6), O1···C9i 3.439 (6), O1···C10i 3.570 (6), O2···C12i 3.611 (6), O2···C13i 3.483 (6) and O2···C14i 3.567 (6) Å [symmetry code: (i) 2 - x, 1 - y, 1 - z].
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 1997b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
(C13H13N2O2)[Ni(C4N2S2)2] | F(000) = 1156 |
Mr = 568.32 | Dx = 1.584 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.2343 (13) Å | Cell parameters from 36 reflections |
b = 26.691 (4) Å | θ = 7.4–14.4° |
c = 12.745 (2) Å | µ = 1.20 mm−1 |
β = 104.510 (16)° | T = 293 K |
V = 2382.4 (7) Å3 | Block, black |
Z = 4 | 0.40 × 0.30 × 0.30 mm |
Bruker P4 diffractometer | 2775 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.043 |
Graphite monochromator | θmax = 25.0°, θmin = 1.8° |
2θ/ω scans | h = −1→8 |
Absorption correction: ψ scan (North et al., 1968) | k = −1→31 |
Tmin = 0.646, Tmax = 0.715 | l = −15→15 |
5502 measured reflections | 3 standard reflections every 97 reflections |
4202 independent reflections | intensity decay: 6.6% |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.124 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0441P)2 + 1.9841P] where P = (Fo2 + 2Fc2)/3 |
4202 reflections | (Δ/σ)max = 0.001 |
308 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.55 e Å−3 |
(C13H13N2O2)[Ni(C4N2S2)2] | V = 2382.4 (7) Å3 |
Mr = 568.32 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.2343 (13) Å | µ = 1.20 mm−1 |
b = 26.691 (4) Å | T = 293 K |
c = 12.745 (2) Å | 0.40 × 0.30 × 0.30 mm |
β = 104.510 (16)° |
Bruker P4 diffractometer | 2775 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.043 |
Tmin = 0.646, Tmax = 0.715 | 3 standard reflections every 97 reflections |
5502 measured reflections | intensity decay: 6.6% |
4202 independent reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.124 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.41 e Å−3 |
4202 reflections | Δρmin = −0.55 e Å−3 |
308 parameters |
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 | ||
Ni1 | 0.26470 (8) | 0.48959 (2) | 0.07147 (4) | 0.04639 (18) | |
S1 | 0.3526 (2) | 0.55562 (5) | 0.16616 (10) | 0.0613 (4) | |
S2 | 0.24845 (17) | 0.52891 (5) | −0.07804 (9) | 0.0501 (3) | |
S3 | 0.18266 (17) | 0.42138 (4) | −0.01909 (9) | 0.0501 (3) | |
S4 | 0.2766 (2) | 0.45348 (5) | 0.22338 (9) | 0.0584 (3) | |
O1 | 0.6681 (6) | 0.43868 (16) | 0.4447 (4) | 0.0966 (14) | |
O2 | 0.8831 (7) | 0.42987 (15) | 0.3554 (3) | 0.0876 (12) | |
N1 | 0.4952 (7) | 0.68572 (18) | 0.1486 (4) | 0.0816 (15) | |
N2 | 0.3347 (8) | 0.65502 (18) | −0.1792 (4) | 0.0811 (14) | |
N3 | 0.1068 (9) | 0.28587 (18) | 0.0303 (4) | 0.0927 (17) | |
N4 | 0.1986 (7) | 0.32979 (18) | 0.3370 (4) | 0.0753 (13) | |
N5 | 0.7817 (7) | 0.45542 (17) | 0.3965 (4) | 0.0647 (12) | |
N6 | 1.0602 (6) | 0.68552 (14) | 0.4157 (3) | 0.0523 (10) | |
C1 | 0.4346 (8) | 0.6482 (2) | 0.1118 (4) | 0.0609 (13) | |
C2 | 0.3642 (6) | 0.60017 (17) | 0.0715 (4) | 0.0501 (11) | |
C3 | 0.3156 (6) | 0.58855 (17) | −0.0364 (4) | 0.0473 (11) | |
C4 | 0.3256 (7) | 0.62569 (19) | −0.1161 (4) | 0.0583 (13) | |
C5 | 0.1356 (8) | 0.3272 (2) | 0.0513 (4) | 0.0618 (13) | |
C6 | 0.1759 (6) | 0.37860 (17) | 0.0813 (4) | 0.0477 (11) | |
C7 | 0.2126 (6) | 0.39294 (17) | 0.1869 (4) | 0.0494 (11) | |
C8 | 0.2054 (7) | 0.35772 (19) | 0.2707 (4) | 0.0568 (13) | |
C9 | 0.9462 (7) | 0.58158 (19) | 0.3389 (4) | 0.0613 (13) | |
H9 | 1.0330 | 0.5957 | 0.3045 | 0.074* | |
C10 | 0.9262 (8) | 0.53067 (19) | 0.3406 (4) | 0.0608 (13) | |
H10 | 0.9982 | 0.5100 | 0.3075 | 0.073* | |
C11 | 0.7982 (7) | 0.51069 (17) | 0.3920 (4) | 0.0517 (11) | |
C12 | 0.6876 (8) | 0.5404 (2) | 0.4396 (4) | 0.0693 (15) | |
H12 | 0.5997 | 0.5262 | 0.4730 | 0.083* | |
C13 | 0.7088 (7) | 0.59123 (19) | 0.4368 (4) | 0.0629 (14) | |
H13 | 0.6343 | 0.6118 | 0.4685 | 0.076* | |
C14 | 0.8384 (7) | 0.61226 (17) | 0.3879 (4) | 0.0504 (11) | |
C15 | 0.8572 (7) | 0.66882 (18) | 0.3887 (4) | 0.0625 (13) | |
H15A | 0.7923 | 0.6818 | 0.3179 | 0.075* | |
H15B | 0.7950 | 0.6827 | 0.4413 | 0.075* | |
C16 | 1.1559 (8) | 0.67962 (18) | 0.5235 (4) | 0.0599 (13) | |
H16 | 1.0944 | 0.6643 | 0.5709 | 0.072* | |
C17 | 1.3343 (8) | 0.6955 (2) | 0.5601 (4) | 0.0687 (15) | |
H17 | 1.3981 | 0.6911 | 0.6325 | 0.082* | |
C18 | 1.4249 (8) | 0.71874 (19) | 0.4887 (5) | 0.0694 (15) | |
H18 | 1.5483 | 0.7311 | 0.5134 | 0.083* | |
C19 | 1.3312 (8) | 0.72311 (19) | 0.3829 (5) | 0.0679 (15) | |
H19 | 1.3929 | 0.7375 | 0.3346 | 0.081* | |
C20 | 1.1436 (9) | 0.70634 (19) | 0.3451 (4) | 0.0645 (14) | |
C21 | 1.0402 (10) | 0.7121 (2) | 0.2316 (4) | 0.100 (2) | |
H21A | 0.9890 | 0.6803 | 0.2033 | 0.150* | |
H21B | 1.1258 | 0.7241 | 0.1907 | 0.150* | |
H21C | 0.9378 | 0.7356 | 0.2263 | 0.150* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0474 (3) | 0.0461 (3) | 0.0470 (3) | 0.0024 (3) | 0.0143 (3) | 0.0010 (3) |
S1 | 0.0812 (9) | 0.0543 (8) | 0.0478 (7) | −0.0042 (7) | 0.0149 (6) | −0.0017 (6) |
S2 | 0.0540 (7) | 0.0480 (7) | 0.0477 (6) | 0.0005 (6) | 0.0118 (5) | 0.0002 (5) |
S3 | 0.0558 (7) | 0.0501 (7) | 0.0452 (6) | −0.0025 (6) | 0.0141 (5) | 0.0014 (5) |
S4 | 0.0750 (9) | 0.0548 (8) | 0.0477 (6) | −0.0006 (7) | 0.0194 (6) | −0.0014 (5) |
O1 | 0.095 (3) | 0.066 (3) | 0.134 (4) | −0.012 (2) | 0.039 (3) | 0.014 (3) |
O2 | 0.117 (4) | 0.053 (2) | 0.095 (3) | 0.007 (2) | 0.029 (3) | −0.007 (2) |
N1 | 0.110 (4) | 0.054 (3) | 0.074 (3) | −0.012 (3) | 0.008 (3) | −0.005 (2) |
N2 | 0.116 (4) | 0.065 (3) | 0.063 (3) | −0.004 (3) | 0.024 (3) | 0.006 (2) |
N3 | 0.152 (5) | 0.053 (3) | 0.073 (3) | −0.025 (3) | 0.029 (3) | −0.001 (2) |
N4 | 0.095 (4) | 0.073 (3) | 0.061 (3) | 0.000 (3) | 0.025 (3) | 0.019 (2) |
N5 | 0.070 (3) | 0.051 (3) | 0.065 (3) | −0.004 (2) | 0.001 (2) | 0.000 (2) |
N6 | 0.062 (3) | 0.040 (2) | 0.060 (2) | 0.0028 (19) | 0.024 (2) | −0.0011 (18) |
C1 | 0.068 (4) | 0.057 (3) | 0.056 (3) | 0.000 (3) | 0.012 (3) | 0.002 (3) |
C2 | 0.049 (3) | 0.045 (3) | 0.056 (3) | −0.003 (2) | 0.013 (2) | −0.005 (2) |
C3 | 0.041 (2) | 0.052 (3) | 0.049 (3) | 0.003 (2) | 0.012 (2) | −0.001 (2) |
C4 | 0.068 (4) | 0.057 (3) | 0.050 (3) | 0.002 (3) | 0.014 (3) | 0.001 (3) |
C5 | 0.079 (4) | 0.056 (3) | 0.050 (3) | −0.008 (3) | 0.016 (3) | 0.005 (2) |
C6 | 0.042 (3) | 0.051 (3) | 0.051 (3) | −0.002 (2) | 0.014 (2) | 0.004 (2) |
C7 | 0.051 (3) | 0.049 (3) | 0.050 (3) | 0.002 (2) | 0.014 (2) | 0.003 (2) |
C8 | 0.059 (3) | 0.056 (3) | 0.055 (3) | 0.001 (3) | 0.014 (2) | 0.002 (3) |
C9 | 0.070 (3) | 0.057 (3) | 0.064 (3) | −0.007 (3) | 0.029 (3) | −0.003 (2) |
C10 | 0.078 (4) | 0.051 (3) | 0.056 (3) | 0.002 (3) | 0.022 (3) | −0.011 (2) |
C11 | 0.056 (3) | 0.041 (3) | 0.052 (3) | −0.004 (2) | 0.001 (2) | −0.004 (2) |
C12 | 0.070 (4) | 0.057 (4) | 0.088 (4) | −0.009 (3) | 0.032 (3) | −0.008 (3) |
C13 | 0.063 (3) | 0.052 (3) | 0.081 (4) | −0.001 (3) | 0.031 (3) | −0.011 (3) |
C14 | 0.053 (3) | 0.044 (3) | 0.052 (3) | 0.001 (2) | 0.008 (2) | −0.001 (2) |
C15 | 0.053 (3) | 0.050 (3) | 0.082 (4) | 0.000 (2) | 0.013 (3) | −0.003 (3) |
C16 | 0.065 (3) | 0.057 (3) | 0.061 (3) | 0.005 (3) | 0.023 (3) | 0.005 (2) |
C17 | 0.076 (4) | 0.073 (4) | 0.055 (3) | 0.008 (3) | 0.013 (3) | −0.007 (3) |
C18 | 0.066 (4) | 0.059 (3) | 0.085 (4) | −0.006 (3) | 0.022 (3) | −0.011 (3) |
C19 | 0.067 (4) | 0.051 (3) | 0.092 (4) | −0.007 (3) | 0.032 (3) | 0.000 (3) |
C20 | 0.093 (4) | 0.047 (3) | 0.056 (3) | 0.013 (3) | 0.025 (3) | 0.003 (2) |
C21 | 0.134 (6) | 0.101 (5) | 0.060 (4) | 0.025 (4) | 0.016 (4) | 0.018 (3) |
Ni1—S1 | 2.1407 (14) | C9—C14 | 1.383 (6) |
Ni1—S4 | 2.1451 (13) | C9—H9 | 0.9300 |
Ni1—S2 | 2.1526 (13) | C10—C11 | 1.369 (7) |
Ni1—S3 | 2.1577 (13) | C10—H10 | 0.9300 |
S1—C2 | 1.711 (5) | C11—C12 | 1.371 (7) |
S2—C3 | 1.710 (5) | C12—C13 | 1.368 (7) |
S3—C6 | 1.725 (4) | C12—H12 | 0.9300 |
S4—C7 | 1.713 (5) | C13—C14 | 1.370 (6) |
O1—N5 | 1.227 (6) | C13—H13 | 0.9300 |
O2—N5 | 1.213 (5) | C14—C15 | 1.515 (6) |
N1—C1 | 1.147 (6) | C15—H15A | 0.9700 |
N2—C4 | 1.135 (6) | C15—H15B | 0.9700 |
N3—C5 | 1.142 (6) | C16—C17 | 1.327 (7) |
N4—C8 | 1.137 (6) | C16—H16 | 0.9300 |
N5—C11 | 1.482 (6) | C17—C18 | 1.394 (7) |
N6—C20 | 1.324 (6) | C17—H17 | 0.9300 |
N6—C16 | 1.384 (6) | C18—C19 | 1.354 (7) |
N6—C15 | 1.490 (6) | C18—H18 | 0.9300 |
C1—C2 | 1.426 (7) | C19—C20 | 1.395 (7) |
C2—C3 | 1.367 (6) | C19—H19 | 0.9300 |
C3—C4 | 1.435 (7) | C20—C21 | 1.461 (7) |
C5—C6 | 1.435 (7) | C21—H21A | 0.9600 |
C6—C7 | 1.360 (6) | C21—H21B | 0.9600 |
C7—C8 | 1.433 (6) | C21—H21C | 0.9600 |
C9—C10 | 1.367 (7) | ||
S1—Ni1—S4 | 85.53 (5) | C10—C11—N5 | 118.5 (5) |
S1—Ni1—S2 | 92.31 (5) | C12—C11—N5 | 119.8 (5) |
S4—Ni1—S2 | 177.38 (6) | C13—C12—C11 | 118.7 (5) |
S1—Ni1—S3 | 177.84 (6) | C13—C12—H12 | 120.6 |
S4—Ni1—S3 | 92.70 (5) | C11—C12—H12 | 120.6 |
S2—Ni1—S3 | 89.49 (5) | C12—C13—C14 | 120.8 (5) |
C2—S1—Ni1 | 103.57 (16) | C12—C13—H13 | 119.6 |
C3—S2—Ni1 | 103.34 (16) | C14—C13—H13 | 119.6 |
C6—S3—Ni1 | 102.53 (16) | C13—C14—C9 | 119.4 (5) |
C7—S4—Ni1 | 103.41 (16) | C13—C14—C15 | 118.4 (4) |
O2—N5—O1 | 124.4 (5) | C9—C14—C15 | 122.2 (4) |
O2—N5—C11 | 118.7 (5) | N6—C15—C14 | 112.4 (4) |
O1—N5—C11 | 116.9 (5) | N6—C15—H15A | 109.1 |
C20—N6—C16 | 121.5 (5) | C14—C15—H15A | 109.1 |
C20—N6—C15 | 124.0 (4) | N6—C15—H15B | 109.1 |
C16—N6—C15 | 114.5 (4) | C14—C15—H15B | 109.1 |
N1—C1—C2 | 176.8 (6) | H15A—C15—H15B | 107.9 |
C3—C2—C1 | 123.0 (4) | C17—C16—N6 | 120.9 (5) |
C3—C2—S1 | 120.4 (4) | C17—C16—H16 | 119.5 |
C1—C2—S1 | 116.5 (3) | N6—C16—H16 | 119.5 |
C2—C3—C4 | 120.7 (4) | C16—C17—C18 | 119.2 (5) |
C2—C3—S2 | 120.3 (4) | C16—C17—H17 | 120.4 |
C4—C3—S2 | 119.0 (3) | C18—C17—H17 | 120.4 |
N2—C4—C3 | 179.6 (6) | C19—C18—C17 | 119.3 (5) |
N3—C5—C6 | 178.0 (6) | C19—C18—H18 | 120.4 |
C7—C6—C5 | 120.6 (4) | C17—C18—H18 | 120.4 |
C7—C6—S3 | 120.9 (4) | C18—C19—C20 | 121.1 (5) |
C5—C6—S3 | 118.5 (3) | C18—C19—H19 | 119.4 |
C6—C7—C8 | 121.2 (4) | C20—C19—H19 | 119.4 |
C6—C7—S4 | 120.4 (4) | N6—C20—C19 | 118.0 (5) |
C8—C7—S4 | 118.3 (4) | N6—C20—C21 | 120.6 (6) |
N4—C8—C7 | 179.6 (6) | C19—C20—C21 | 121.4 (6) |
C10—C9—C14 | 120.5 (5) | C20—C21—H21A | 109.5 |
C10—C9—H9 | 119.8 | C20—C21—H21B | 109.5 |
C14—C9—H9 | 119.8 | H21A—C21—H21B | 109.5 |
C9—C10—C11 | 118.8 (5) | C20—C21—H21C | 109.5 |
C9—C10—H10 | 120.6 | H21A—C21—H21C | 109.5 |
C11—C10—H10 | 120.6 | H21B—C21—H21C | 109.5 |
C10—C11—C12 | 121.7 (5) | ||
S4—Ni1—S1—C2 | −179.74 (17) | Ni1—S4—C7—C8 | −179.9 (3) |
S2—Ni1—S1—C2 | −1.23 (17) | C6—C7—C8—N4 | −80 (70) |
S3—Ni1—S1—C2 | 145.3 (15) | S4—C7—C8—N4 | 102 (70) |
S1—Ni1—S2—C3 | 0.56 (16) | C14—C9—C10—C11 | −0.2 (8) |
S4—Ni1—S2—C3 | 35.0 (13) | C9—C10—C11—C12 | 1.3 (8) |
S3—Ni1—S2—C3 | −178.24 (16) | C9—C10—C11—N5 | −178.1 (4) |
S1—Ni1—S3—C6 | 34.6 (16) | O2—N5—C11—C10 | 0.6 (7) |
S4—Ni1—S3—C6 | −0.27 (16) | O1—N5—C11—C10 | 178.8 (5) |
S2—Ni1—S3—C6 | −178.83 (16) | O2—N5—C11—C12 | −178.8 (5) |
S1—Ni1—S4—C7 | −179.58 (17) | O1—N5—C11—C12 | −0.7 (7) |
S2—Ni1—S4—C7 | 145.9 (12) | C10—C11—C12—C13 | −1.1 (8) |
S3—Ni1—S4—C7 | −0.82 (17) | N5—C11—C12—C13 | 178.3 (5) |
N1—C1—C2—C3 | −156 (11) | C11—C12—C13—C14 | −0.2 (8) |
N1—C1—C2—S1 | 21 (12) | C12—C13—C14—C9 | 1.3 (8) |
Ni1—S1—C2—C3 | 1.9 (4) | C12—C13—C14—C15 | −179.3 (5) |
Ni1—S1—C2—C1 | −175.2 (3) | C10—C9—C14—C13 | −1.1 (8) |
C1—C2—C3—C4 | −2.8 (7) | C10—C9—C14—C15 | 179.5 (5) |
S1—C2—C3—C4 | −179.8 (4) | C20—N6—C15—C14 | 109.5 (5) |
C1—C2—C3—S2 | 175.3 (4) | C16—N6—C15—C14 | −73.2 (5) |
S1—C2—C3—S2 | −1.7 (6) | C13—C14—C15—N6 | 135.9 (5) |
Ni1—S2—C3—C2 | 0.5 (4) | C9—C14—C15—N6 | −44.7 (7) |
Ni1—S2—C3—C4 | 178.6 (3) | C20—N6—C16—C17 | 1.1 (7) |
C2—C3—C4—N2 | 85 (81) | C15—N6—C16—C17 | −176.2 (5) |
S2—C3—C4—N2 | −93 (81) | N6—C16—C17—C18 | 0.5 (8) |
N3—C5—C6—C7 | −29 (19) | C16—C17—C18—C19 | −2.2 (8) |
N3—C5—C6—S3 | 150 (19) | C17—C18—C19—C20 | 2.3 (8) |
Ni1—S3—C6—C7 | 1.8 (4) | C16—N6—C20—C19 | −1.1 (7) |
Ni1—S3—C6—C5 | −176.6 (4) | C15—N6—C20—C19 | 176.0 (4) |
C5—C6—C7—C8 | −2.3 (7) | C16—N6—C20—C21 | 179.8 (5) |
S3—C6—C7—C8 | 179.4 (4) | C15—N6—C20—C21 | −3.1 (7) |
C5—C6—C7—S4 | 175.5 (4) | C18—C19—C20—N6 | −0.6 (8) |
S3—C6—C7—S4 | −2.8 (6) | C18—C19—C20—C21 | 178.5 (5) |
Ni1—S4—C7—C6 | 2.2 (4) |
Experimental details
Crystal data | |
Chemical formula | (C13H13N2O2)[Ni(C4N2S2)2] |
Mr | 568.32 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.2343 (13), 26.691 (4), 12.745 (2) |
β (°) | 104.510 (16) |
V (Å3) | 2382.4 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.20 |
Crystal size (mm) | 0.40 × 0.30 × 0.30 |
Data collection | |
Diffractometer | Bruker P4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.646, 0.715 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5502, 4202, 2775 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.124, 1.04 |
No. of reflections | 4202 |
No. of parameters | 308 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.41, −0.55 |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL (Sheldrick, 1997b), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL.
Ni1—S1 | 2.1407 (14) | S1—C2 | 1.711 (5) |
Ni1—S4 | 2.1451 (13) | S2—C3 | 1.710 (5) |
Ni1—S2 | 2.1526 (13) | S3—C6 | 1.725 (4) |
Ni1—S3 | 2.1577 (13) | S4—C7 | 1.713 (5) |
S1—Ni1—S4 | 85.53 (5) | N1—C1—C2 | 176.8 (6) |
S1—Ni1—S2 | 92.31 (5) | N2—C4—C3 | 179.6 (6) |
S4—Ni1—S3 | 92.70 (5) | N3—C5—C6 | 178.0 (6) |
S2—Ni1—S3 | 89.49 (5) | N4—C8—C7 | 179.6 (6) |
Recently, considerable interest has been focused on low-dimensional molecular solids with novel magnetic properties, such as spin-Peierls transitions (Brown et al., 1998) and room-temperature spin bistability (Fujita & Awaga, 1999). Our aim is to construct quasi-one-dimensional molecule-based magnetic materials formed by platelike maleonitriledithiolene anionic metal complexes [M(mnt)2]- (M is NiIII, PdIII or PtIII). These types of low-dimensional materials are associated with columnar crystallographic packing. Previous work has shown that the geometry of the counter-cations strongly influences the stacking structure of this type of material. Therefore, it is important to select particular counter-cations in order to obtain columnar crystallographic packing. The ground-state conformations of benzylpyridinium derivatives have been extensively investigated by many techniques, and results to date have indicated that the spatial orientation of the benzene and pyridine rings depends on both the electronic and the steric properties of the substituents on the aryl rings (Bulgarevich et al., 1994). The different conformations available to benzylpyridinium derivatives may lead to differences in the geometry of the cations, sufficient to influence the stacking structures of the complexes in the solid state. As a result, the ion-pair complexes consisting of [M(mnt)2]- anions and benzylpyridinium-derived cations present a unique opportunity for the systematic investigation of the fundamental relationship between the stacking structure in the solid and the substituents on the aryl rings. To test this idea, we prepared a series of complexes by systematically varying the substituents on the aryl rings, and found that it is possible to obtain completely separated anions and cations in columnar stacking structures. Herein, we report the crystal structure of the title compound, (I), which has columnar packing. \sch
In the anion of (I), the Ni atom exhibits square-planar coordination geometry involving four S atoms, and the five-membered nickel-containing rings are slightly puckered (Fig. 1), as has been found in other [M(mnt)2]n- structures (Plumlee et al., 1975). The average S—Ni—S bond angle within the five-membered ring is 92.50 (5)° and the average Ni—S bond distance is 2.1477 (13) Å. Other chemically equivalent but crystallographically non-equivalent bond distances within the anion differ by less than three s.u.'s and compare well with those found in [Ni(mnt)2]- complexes (Brunn et al., 1987). The anion is non-planar and the CN groups bend away from the plane of the four S atoms. The CN group with the largest deviation is C1≡N1, and the deviations from the plane defined by the four S atoms are 0.294 (6) Å for N1 and 0.167 (6) Å for C1. The cation adopts a conformation where the dihedral angle between the benzene ring and the C14/C15/N6 reference plane is 44.5 (4)°, and the pyridine ring is twisted towards the reference plane with a dihedral angle of 72.3 (4)°.
The most prominent general structural features of the complex are the completely segregated stacked columns of [Ni(mnt)2]- anions and 1-(4-nitrobenzyl)-2-methylpyridinium cations, as revealed by the projection along the crystallographic a axis in Fig. 2. Completely segregated stacked columns of [Ni(mnt)2]- anions have been infrequently reported (Hobi et al., 1996). The Ni···Ni distances are alternately 3.847 (1) and 4.281 (1) Å within the [Ni(mnt)2]- column. The nearest Ni···Ni contact between [Ni(mnt)2]- columns is much larger at 10.6 Å, and is larger than the Ni···Ni distance within the [Ni(mnt)2]- column. These results indicate that, compared with intracolumnar interactions, the Ni···Ni magnetic exchange interactions between columns may be neglected. Within the 1-(4-nitrobenzyl)-2-methylbenzylpyridinium cation column, the nitro group of one cation is stacked over the benzene ring of an adjacent cation (Fig. 3). This type of packing structure is often found in nitrobenzene derivatives (Harrowfield et al., 1998). The shorter contacts between adjacent nitro groups and benzene rings are: N5···C9i 3.591 (6), N5···C10i 3.505 (6), N5···C11i 3.636 (6), O1···C9i 3.439 (6), O1···C10i 3.570 (6), O2···C12i 3.611 (6), O2···C13i 3.483 (6) and O2···C14i 3.567 (6) Å [symmetry code: (i) 2 - x, 1 - y, 1 - z].