Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803005270/ww6067sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803005270/ww6067Isup2.hkl |
CCDC reference: 197280
Disodium maleonitriledithiolate (Na2mnt) was prepared following the procedure of Davison & Holm (1967). N-(2-Fluoro-4-bromobenzyl)pyridinium chloride was prepared by reacting 2-fluoro-4-benzyl chloride with 1.5 equivalent of pyridine in refluxing acetone for 4 h. The white microcrystalline product was filtered off and washed with acetone and diethyl ether in turn; the yield is more than 86% after drying in a vaccum. A similar method for synthesizing [Bu4N]2[Pd(mnt)2] (Davison & Holm, 1967) was used to prepare the title compound, (I). Good shaped black single crystals suitable for X-ray analysis were obtained by diffusing diethyl ether into an acetonitrile solution of complex (I) for about 3 d.
All H atoms were placed in geometrically calculated positions (C—H = 0.93 and 0.97 Å), with Uiso = 1.2Ueq(parent atom).
Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL.
(C12H10BrFN)2[Pd(C4N2S2)2] | Z = 1 |
Mr = 921.00 | F(000) = 452 |
Triclinic, P1 | Dx = 1.830 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.1140 (18) Å | Cell parameters from 25 reflections |
b = 11.035 (3) Å | θ = 3.1–27.5° |
c = 11.851 (3) Å | µ = 3.24 mm−1 |
α = 69.564 (4)° | T = 293 K |
β = 89.016 (4)° | Block, black |
γ = 74.151 (4)° | 0.15 × 0.10 × 0.10 mm |
V = 835.5 (4) Å3 |
Siemens CCD area-detector diffractometer | 2907 independent reflections |
Radiation source: fine-focus sealed tube | 2348 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: empirical (using intensity measurements) (North et al., 1984) | h = −7→8 |
Tmin = 0.665, Tmax = 0.728 | k = −13→13 |
4372 measured reflections | l = −13→14 |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.065 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.025P)2] where P = (Fo2 + 2Fc2)/3 |
2907 reflections | (Δ/σ)max = 0.001 |
214 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.47 e Å−3 |
(C12H10BrFN)2[Pd(C4N2S2)2] | γ = 74.151 (4)° |
Mr = 921.00 | V = 835.5 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.1140 (18) Å | Mo Kα radiation |
b = 11.035 (3) Å | µ = 3.24 mm−1 |
c = 11.851 (3) Å | T = 293 K |
α = 69.564 (4)° | 0.15 × 0.10 × 0.10 mm |
β = 89.016 (4)° |
Siemens CCD area-detector diffractometer | 2907 independent reflections |
Absorption correction: empirical (using intensity measurements) (North et al., 1984) | 2348 reflections with I > 2σ(I) |
Tmin = 0.665, Tmax = 0.728 | Rint = 0.016 |
4372 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.065 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.37 e Å−3 |
2907 reflections | Δρmin = −0.47 e Å−3 |
214 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 | ||
Pd1 | 0.5000 | 0.5000 | 0.5000 | 0.04301 (12) | |
S1 | 0.40863 (14) | 0.72963 (9) | 0.44522 (7) | 0.0547 (2) | |
S2 | 0.58998 (13) | 0.47912 (8) | 0.69237 (7) | 0.0506 (2) | |
Br1 | 0.66831 (6) | −0.03283 (4) | 0.85503 (3) | 0.06649 (14) | |
N1 | 0.2957 (5) | 0.9925 (3) | 0.5777 (3) | 0.0779 (10) | |
N2 | 0.5539 (5) | 0.6785 (3) | 0.8871 (3) | 0.0787 (10) | |
N3 | 1.1281 (4) | 0.4618 (3) | 0.7710 (2) | 0.0445 (6) | |
C1 | 0.3641 (5) | 0.8849 (4) | 0.5803 (3) | 0.0556 (9) | |
C2 | 0.4384 (5) | 0.7496 (3) | 0.5823 (3) | 0.0469 (8) | |
C3 | 0.5145 (5) | 0.6450 (3) | 0.6852 (3) | 0.0464 (8) | |
C4 | 0.5342 (5) | 0.6662 (4) | 0.7970 (3) | 0.0558 (9) | |
C5 | 1.1262 (6) | 0.5449 (4) | 0.8308 (3) | 0.0592 (10) | |
H5A | 1.1843 | 0.5097 | 0.9095 | 0.071* | |
C6 | 1.0414 (6) | 0.6789 (4) | 0.7787 (4) | 0.0700 (11) | |
H6A | 1.0370 | 0.7350 | 0.8223 | 0.084* | |
C7 | 0.9619 (5) | 0.7320 (4) | 0.6617 (3) | 0.0598 (10) | |
H7A | 0.9053 | 0.8245 | 0.6246 | 0.072* | |
C8 | 0.9666 (6) | 0.6486 (4) | 0.6008 (3) | 0.0663 (11) | |
H8A | 0.9125 | 0.6828 | 0.5212 | 0.080* | |
C9 | 1.0518 (6) | 0.5128 (4) | 0.6572 (3) | 0.0628 (10) | |
H9A | 1.0561 | 0.4553 | 0.6149 | 0.075* | |
C10 | 1.2258 (5) | 0.3150 (3) | 0.8276 (3) | 0.0539 (9) | |
H10A | 1.2784 | 0.2953 | 0.9091 | 0.065* | |
H10B | 1.3346 | 0.2899 | 0.7820 | 0.065* | |
C11 | 1.0879 (5) | 0.2314 (3) | 0.8324 (3) | 0.0433 (8) | |
C12 | 0.9332 (5) | 0.2349 (3) | 0.9027 (3) | 0.0457 (8) | |
C13 | 0.8074 (5) | 0.1583 (3) | 0.9133 (3) | 0.0488 (8) | |
H13A | 0.7046 | 0.1627 | 0.9626 | 0.059* | |
C14 | 0.8398 (5) | 0.0741 (3) | 0.8474 (3) | 0.0471 (8) | |
C15 | 0.9913 (5) | 0.0675 (3) | 0.7751 (3) | 0.0497 (8) | |
H15A | 1.0103 | 0.0108 | 0.7309 | 0.060* | |
C16 | 1.1159 (5) | 0.1459 (3) | 0.7683 (3) | 0.0513 (9) | |
H16A | 1.2200 | 0.1409 | 0.7200 | 0.062* | |
F1 | 0.9026 (3) | 0.3201 (2) | 0.96467 (17) | 0.0675 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.0417 (2) | 0.0389 (2) | 0.0416 (2) | −0.01027 (16) | −0.00154 (16) | −0.00693 (16) |
S1 | 0.0691 (6) | 0.0409 (5) | 0.0431 (5) | −0.0092 (4) | −0.0043 (4) | −0.0062 (4) |
S2 | 0.0532 (6) | 0.0446 (5) | 0.0447 (5) | −0.0120 (4) | −0.0065 (4) | −0.0059 (4) |
Br1 | 0.0639 (3) | 0.0558 (3) | 0.0715 (3) | −0.0237 (2) | −0.0084 (2) | −0.0070 (2) |
N1 | 0.094 (3) | 0.058 (2) | 0.077 (2) | −0.0102 (19) | 0.018 (2) | −0.0271 (19) |
N2 | 0.098 (3) | 0.093 (3) | 0.061 (2) | −0.046 (2) | 0.006 (2) | −0.032 (2) |
N3 | 0.0405 (16) | 0.0455 (16) | 0.0451 (16) | −0.0125 (13) | −0.0003 (13) | −0.0130 (13) |
C1 | 0.062 (2) | 0.052 (2) | 0.050 (2) | −0.0154 (19) | 0.0136 (18) | −0.0154 (18) |
C2 | 0.045 (2) | 0.0429 (19) | 0.0492 (19) | −0.0125 (16) | 0.0071 (16) | −0.0131 (16) |
C3 | 0.042 (2) | 0.050 (2) | 0.0463 (19) | −0.0144 (16) | 0.0048 (16) | −0.0158 (17) |
C4 | 0.057 (2) | 0.058 (2) | 0.050 (2) | −0.0235 (19) | 0.0011 (19) | −0.0120 (19) |
C5 | 0.073 (3) | 0.058 (2) | 0.049 (2) | −0.018 (2) | −0.0117 (19) | −0.0224 (19) |
C6 | 0.092 (3) | 0.052 (2) | 0.068 (3) | −0.015 (2) | 0.001 (2) | −0.028 (2) |
C7 | 0.058 (2) | 0.047 (2) | 0.069 (3) | −0.0167 (19) | 0.006 (2) | −0.014 (2) |
C8 | 0.081 (3) | 0.062 (3) | 0.047 (2) | −0.019 (2) | −0.008 (2) | −0.009 (2) |
C9 | 0.080 (3) | 0.060 (2) | 0.046 (2) | −0.014 (2) | −0.005 (2) | −0.0204 (19) |
C10 | 0.048 (2) | 0.047 (2) | 0.058 (2) | −0.0044 (17) | −0.0055 (18) | −0.0138 (17) |
C11 | 0.0375 (19) | 0.0410 (18) | 0.0430 (18) | −0.0044 (15) | −0.0082 (15) | −0.0095 (15) |
C12 | 0.048 (2) | 0.0423 (19) | 0.0395 (18) | −0.0036 (16) | −0.0044 (16) | −0.0129 (16) |
C13 | 0.044 (2) | 0.049 (2) | 0.0408 (18) | −0.0046 (17) | 0.0011 (16) | −0.0074 (16) |
C14 | 0.045 (2) | 0.0385 (19) | 0.0446 (18) | −0.0077 (16) | −0.0097 (16) | −0.0012 (16) |
C15 | 0.050 (2) | 0.044 (2) | 0.053 (2) | −0.0060 (17) | −0.0011 (17) | −0.0197 (17) |
C16 | 0.046 (2) | 0.051 (2) | 0.0483 (19) | −0.0053 (17) | 0.0034 (17) | −0.0138 (17) |
F1 | 0.0767 (15) | 0.0706 (14) | 0.0653 (13) | −0.0182 (12) | 0.0116 (11) | −0.0388 (12) |
Pd1—S1 | 2.2872 (11) | C7—C8 | 1.348 (5) |
Pd1—S1i | 2.2872 (11) | C7—H7A | 0.9300 |
Pd1—S2 | 2.2941 (10) | C8—C9 | 1.370 (5) |
Pd1—S2i | 2.2941 (10) | C8—H8A | 0.9300 |
S1—C2 | 1.738 (3) | C9—H9A | 0.9300 |
S2—C3 | 1.732 (3) | C10—C11 | 1.507 (4) |
Br1—C14 | 1.897 (3) | C10—H10A | 0.9700 |
N1—C1 | 1.143 (4) | C10—H10B | 0.9700 |
N2—C4 | 1.138 (4) | C11—C12 | 1.369 (4) |
N3—C9 | 1.326 (4) | C11—C16 | 1.378 (4) |
N3—C5 | 1.337 (4) | C12—F1 | 1.355 (3) |
N3—C10 | 1.484 (4) | C12—C13 | 1.366 (4) |
C1—C2 | 1.434 (5) | C13—C14 | 1.382 (4) |
C2—C3 | 1.346 (4) | C13—H13A | 0.9300 |
C3—C4 | 1.439 (5) | C14—C15 | 1.368 (4) |
C5—C6 | 1.349 (5) | C15—C16 | 1.381 (4) |
C5—H5A | 0.9300 | C15—H15A | 0.9300 |
C6—C7 | 1.365 (5) | C16—H16A | 0.9300 |
C6—H6A | 0.9300 | ||
S1—Pd1—S1i | 180.0 | C7—C8—H8A | 120.3 |
S1—Pd1—S2 | 89.56 (3) | C9—C8—H8A | 120.3 |
S1i—Pd1—S2 | 90.44 (3) | N3—C9—C8 | 121.2 (3) |
S1—Pd1—S2i | 90.44 (3) | N3—C9—H9A | 119.4 |
S1i—Pd1—S2i | 89.56 (3) | C8—C9—H9A | 119.4 |
S2—Pd1—S2i | 180.0 | N3—C10—C11 | 112.4 (3) |
C2—S1—Pd1 | 102.19 (11) | N3—C10—H10A | 109.1 |
C3—S2—Pd1 | 102.16 (11) | C11—C10—H10A | 109.1 |
C9—N3—C5 | 119.4 (3) | N3—C10—H10B | 109.1 |
C9—N3—C10 | 119.7 (3) | C11—C10—H10B | 109.1 |
C5—N3—C10 | 120.9 (3) | H10A—C10—H10B | 107.9 |
N1—C1—C2 | 176.6 (4) | C12—C11—C16 | 117.5 (3) |
C3—C2—C1 | 121.8 (3) | C12—C11—C10 | 121.4 (3) |
C3—C2—S1 | 122.8 (3) | C16—C11—C10 | 121.1 (3) |
C1—C2—S1 | 115.3 (2) | F1—C12—C11 | 117.9 (3) |
C2—C3—C4 | 120.8 (3) | F1—C12—C13 | 118.2 (3) |
C2—C3—S2 | 122.8 (2) | C11—C12—C13 | 123.9 (3) |
C4—C3—S2 | 116.3 (3) | C12—C13—C14 | 117.0 (3) |
N2—C4—C3 | 177.6 (4) | C12—C13—H13A | 121.5 |
N3—C5—C6 | 121.0 (3) | C14—C13—H13A | 121.5 |
N3—C5—H5A | 119.5 | C15—C14—C13 | 121.5 (3) |
C6—C5—H5A | 119.5 | C15—C14—Br1 | 119.0 (3) |
C5—C6—C7 | 119.9 (3) | C13—C14—Br1 | 119.5 (3) |
C5—C6—H6A | 120.0 | C14—C15—C16 | 119.4 (3) |
C7—C6—H6A | 120.0 | C14—C15—H15A | 120.3 |
C8—C7—C6 | 119.0 (3) | C16—C15—H15A | 120.3 |
C8—C7—H7A | 120.5 | C11—C16—C15 | 120.8 (3) |
C6—C7—H7A | 120.5 | C11—C16—H16A | 119.6 |
C7—C8—C9 | 119.4 (3) | C15—C16—H16A | 119.6 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6A···F1ii | 0.93 | 2.40 | 3.079 (4) | 130 |
Symmetry code: (ii) −x+2, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | (C12H10BrFN)2[Pd(C4N2S2)2] |
Mr | 921.00 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.1140 (18), 11.035 (3), 11.851 (3) |
α, β, γ (°) | 69.564 (4), 89.016 (4), 74.151 (4) |
V (Å3) | 835.5 (4) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 3.24 |
Crystal size (mm) | 0.15 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Siemens CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (North et al., 1984) |
Tmin, Tmax | 0.665, 0.728 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4372, 2907, 2348 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.065, 1.12 |
No. of reflections | 2907 |
No. of parameters | 214 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.47 |
Computer programs: SMART (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6A···F1i | 0.93 | 2.40 | 3.079 (4) | 130 |
Symmetry code: (i) −x+2, −y+1, −z+2. |
Recently, one-dimensional (1-D) compounds have been attracting widespread attention because of their novel physical properties, such as spin-Peierls transition (Bray et al., 1975), spin-charge separation states (Lorenz et al., 2002), and molecular bistabilities (Fujita et al., 1999), and so on. Furthermore, more and more new quantum effects were observed in 1-D spin systems (Caneschi et al., 2001; Shiramura et al., 1998).
In current studies, we have developed a new class of [R-BzPy][Ni(mnt)2] salt, where [R-BzPy]+ represents a derivative of benzylpyridinium, as building blocks to construct a low-dimensional molecular solid (Ren, Meng, Song, Hu et al., 2002; Ren, Meng, Song, Lu et al., 2002; Xie, Ren, Song, Zhang et al., 2002; Xie, Ren, Song, Zou & Meng, 2002; Xie et al., 2003), and found: (a) all of [R-BzPy][Ni(mnt)2] compounds stacking with well separated columns of anions and cations in the solid state, in which [Ni(mnt)2]- anions form a spaced 1-D magnetic chain of s = 1/2 along the direction of the anion column. (b) The topology and size of the [R-BzPy]+ ion, which is related to the molecular conformation of [R-BzPy]+ ion, can be modulated by systematically variation of the substituents in aromatic rings. Therefore, the stacking pattern of those complexes can be finely tuned through controlling the molecular conformation of [R-BzPy]+ ion. (c) The magnetic coupled interactions in these systems are very sensitive to intermolecular separations. A series of complexes obtained, which exist almost same stacking structures but slight different intermolecular spaces, exhibit magnetic diversity, some complexes reveal the unusual phase transition spin-Peierls-like transition. In order to further understand the relationship between magnetic properties and the stacking structures in these types of complexes, we have pursued the study of the complex, [BrFBzPy]2[Pd(mnt)2], (I).
The asymmetric unit of (I) is composed of one N-(2-fluoro-4-bromobenzyl)pyridinium cation and half a [Pd(mnt)2]2- anion (Fig. 1). For the anion, the Pd2+ ion occupies in an inversion center, which is surrounded by four S atoms of two mnt2- ligands, and exhibits a square-planar coordination geometry. The Pd—S distances are in the range 2.2872 (11)–2.2941 (10) Å, with S—Pd—S angles of between 89.56 (3) and 90.44 (3)° (Table 1). These results are in agreement with those of corresponding [Pd(mnt)2]2--containing complexes (Bois et al., 1998). The anionic motif is almost planar, the N atoms of the CN groups being somewhat bent away from the plane, and atoms N1 and N2 deviate from the S4 plane by 0.64 and 0.43 Å, respectively. As for the cations, the pyridine and benzene rings twist with respect to each other, which is similar to the situation in an [Ni(mnt)2]- series reported by us earlier (Ren, Meng, Song, Hu et al., 2002), and the dihedral angles between the reference plane, N3/C10/C11, and the benzene and pyridine rings are 65.73 (16) and 59.7 (3)°, respectively. There are hydrogen-bonding interactions between F1 and adjacent C6 atoms, thus two adjacent cations dimerize through hydrogen-bonding interactions (Fig. 2). The anions and cations form alternating layers, which are nearly parallel to the bc plane of the crystallographic unit cell (Fig. 3).