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In the title salt, (C12H10BrFN)2[Pd(C4N2S2)2] or [N-(2-fluoro-4-bromo­benzyl)­pyridinium]2[Pd(mnt)2], where mnt2− denotes maleo­nitrile­di­thiol­ate, the Pd2+ ion is coordinated by four S atoms of two mnt2− ligands in a planar geometry. The asymmetric unit is composed of one N-(2-fluoro-4-bromo­benzyl)­pyridinium cation and one-half [Pd(mnt)2]2− anion. The adjacent counter-cations form dimers by Cpy—H...FAr hydrogen-bonding interactions. Anions and cations stack in alternating layers which are nearly parallel to the bc plane of the crystallographic unit cell.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803005270/ww6067sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803005270/ww6067Isup2.hkl
Contains datablock I

CCDC reference: 197280

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.030
  • wR factor = 0.065
  • Data-to-parameter ratio = 13.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(1) - C(2) = 1.43 Ang. PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(3) - C(4) = 1.44 Ang.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check

Comment top

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).

Experimental top

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.

Refinement top

All H atoms were placed in geometrically calculated positions (C—H = 0.93 and 0.97 Å), with Uiso = 1.2Ueq(parent atom).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The structure of complex (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. The hydrogen-bonding dimer between adjacent cations.
[Figure 3] Fig. 3. The layered packing of alternating anions and cations for the complex (I).
Bis[N-(2-fluoro-4-bromobenzyl)pyridinium] bis(maleonitriledithiolato)palladium(II) top
Crystal data top
(C12H10BrFN)2[Pd(C4N2S2)2]Z = 1
Mr = 921.00F(000) = 452
Triclinic, P1Dx = 1.830 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.1140 (18) ÅCell parameters from 25 reflections
b = 11.035 (3) Åθ = 3.1–27.5°
c = 11.851 (3) ŵ = 3.24 mm1
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
Data collection top
Siemens CCD area-detector
diffractometer
2907 independent reflections
Radiation source: fine-focus sealed tube2348 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.016
ω scansθmax = 25.0°, θmin = 1.8°
Absorption correction: empirical (using intensity measurements)
(North et al., 1984)
h = 78
Tmin = 0.665, Tmax = 0.728k = 1313
4372 measured reflectionsl = 1314
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.065H-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 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.47 e Å3
Crystal data top
(C12H10BrFN)2[Pd(C4N2S2)2]γ = 74.151 (4)°
Mr = 921.00V = 835.5 (4) Å3
Triclinic, P1Z = 1
a = 7.1140 (18) ÅMo Kα radiation
b = 11.035 (3) ŵ = 3.24 mm1
c = 11.851 (3) ÅT = 293 K
α = 69.564 (4)°0.15 × 0.10 × 0.10 mm
β = 89.016 (4)°
Data collection top
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 = 0.728Rint = 0.016
4372 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.065H-atom parameters constrained
S = 1.12Δρmax = 0.37 e Å3
2907 reflectionsΔρmin = 0.47 e Å3
214 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Pd10.50000.50000.50000.04301 (12)
S10.40863 (14)0.72963 (9)0.44522 (7)0.0547 (2)
S20.58998 (13)0.47912 (8)0.69237 (7)0.0506 (2)
Br10.66831 (6)0.03283 (4)0.85503 (3)0.06649 (14)
N10.2957 (5)0.9925 (3)0.5777 (3)0.0779 (10)
N20.5539 (5)0.6785 (3)0.8871 (3)0.0787 (10)
N31.1281 (4)0.4618 (3)0.7710 (2)0.0445 (6)
C10.3641 (5)0.8849 (4)0.5803 (3)0.0556 (9)
C20.4384 (5)0.7496 (3)0.5823 (3)0.0469 (8)
C30.5145 (5)0.6450 (3)0.6852 (3)0.0464 (8)
C40.5342 (5)0.6662 (4)0.7970 (3)0.0558 (9)
C51.1262 (6)0.5449 (4)0.8308 (3)0.0592 (10)
H5A1.18430.50970.90950.071*
C61.0414 (6)0.6789 (4)0.7787 (4)0.0700 (11)
H6A1.03700.73500.82230.084*
C70.9619 (5)0.7320 (4)0.6617 (3)0.0598 (10)
H7A0.90530.82450.62460.072*
C80.9666 (6)0.6486 (4)0.6008 (3)0.0663 (11)
H8A0.91250.68280.52120.080*
C91.0518 (6)0.5128 (4)0.6572 (3)0.0628 (10)
H9A1.05610.45530.61490.075*
C101.2258 (5)0.3150 (3)0.8276 (3)0.0539 (9)
H10A1.27840.29530.90910.065*
H10B1.33460.28990.78200.065*
C111.0879 (5)0.2314 (3)0.8324 (3)0.0433 (8)
C120.9332 (5)0.2349 (3)0.9027 (3)0.0457 (8)
C130.8074 (5)0.1583 (3)0.9133 (3)0.0488 (8)
H13A0.70460.16270.96260.059*
C140.8398 (5)0.0741 (3)0.8474 (3)0.0471 (8)
C150.9913 (5)0.0675 (3)0.7751 (3)0.0497 (8)
H15A1.01030.01080.73090.060*
C161.1159 (5)0.1459 (3)0.7683 (3)0.0513 (9)
H16A1.22000.14090.72000.062*
F10.9026 (3)0.3201 (2)0.96467 (17)0.0675 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.0417 (2)0.0389 (2)0.0416 (2)0.01027 (16)0.00154 (16)0.00693 (16)
S10.0691 (6)0.0409 (5)0.0431 (5)0.0092 (4)0.0043 (4)0.0062 (4)
S20.0532 (6)0.0446 (5)0.0447 (5)0.0120 (4)0.0065 (4)0.0059 (4)
Br10.0639 (3)0.0558 (3)0.0715 (3)0.0237 (2)0.0084 (2)0.0070 (2)
N10.094 (3)0.058 (2)0.077 (2)0.0102 (19)0.018 (2)0.0271 (19)
N20.098 (3)0.093 (3)0.061 (2)0.046 (2)0.006 (2)0.032 (2)
N30.0405 (16)0.0455 (16)0.0451 (16)0.0125 (13)0.0003 (13)0.0130 (13)
C10.062 (2)0.052 (2)0.050 (2)0.0154 (19)0.0136 (18)0.0154 (18)
C20.045 (2)0.0429 (19)0.0492 (19)0.0125 (16)0.0071 (16)0.0131 (16)
C30.042 (2)0.050 (2)0.0463 (19)0.0144 (16)0.0048 (16)0.0158 (17)
C40.057 (2)0.058 (2)0.050 (2)0.0235 (19)0.0011 (19)0.0120 (19)
C50.073 (3)0.058 (2)0.049 (2)0.018 (2)0.0117 (19)0.0224 (19)
C60.092 (3)0.052 (2)0.068 (3)0.015 (2)0.001 (2)0.028 (2)
C70.058 (2)0.047 (2)0.069 (3)0.0167 (19)0.006 (2)0.014 (2)
C80.081 (3)0.062 (3)0.047 (2)0.019 (2)0.008 (2)0.009 (2)
C90.080 (3)0.060 (2)0.046 (2)0.014 (2)0.005 (2)0.0204 (19)
C100.048 (2)0.047 (2)0.058 (2)0.0044 (17)0.0055 (18)0.0138 (17)
C110.0375 (19)0.0410 (18)0.0430 (18)0.0044 (15)0.0082 (15)0.0095 (15)
C120.048 (2)0.0423 (19)0.0395 (18)0.0036 (16)0.0044 (16)0.0129 (16)
C130.044 (2)0.049 (2)0.0408 (18)0.0046 (17)0.0011 (16)0.0074 (16)
C140.045 (2)0.0385 (19)0.0446 (18)0.0077 (16)0.0097 (16)0.0012 (16)
C150.050 (2)0.044 (2)0.053 (2)0.0060 (17)0.0011 (17)0.0197 (17)
C160.046 (2)0.051 (2)0.0483 (19)0.0053 (17)0.0034 (17)0.0138 (17)
F10.0767 (15)0.0706 (14)0.0653 (13)0.0182 (12)0.0116 (11)0.0388 (12)
Geometric parameters (Å, º) top
Pd1—S12.2872 (11)C7—C81.348 (5)
Pd1—S1i2.2872 (11)C7—H7A0.9300
Pd1—S22.2941 (10)C8—C91.370 (5)
Pd1—S2i2.2941 (10)C8—H8A0.9300
S1—C21.738 (3)C9—H9A0.9300
S2—C31.732 (3)C10—C111.507 (4)
Br1—C141.897 (3)C10—H10A0.9700
N1—C11.143 (4)C10—H10B0.9700
N2—C41.138 (4)C11—C121.369 (4)
N3—C91.326 (4)C11—C161.378 (4)
N3—C51.337 (4)C12—F11.355 (3)
N3—C101.484 (4)C12—C131.366 (4)
C1—C21.434 (5)C13—C141.382 (4)
C2—C31.346 (4)C13—H13A0.9300
C3—C41.439 (5)C14—C151.368 (4)
C5—C61.349 (5)C15—C161.381 (4)
C5—H5A0.9300C15—H15A0.9300
C6—C71.365 (5)C16—H16A0.9300
C6—H6A0.9300
S1—Pd1—S1i180.0C7—C8—H8A120.3
S1—Pd1—S289.56 (3)C9—C8—H8A120.3
S1i—Pd1—S290.44 (3)N3—C9—C8121.2 (3)
S1—Pd1—S2i90.44 (3)N3—C9—H9A119.4
S1i—Pd1—S2i89.56 (3)C8—C9—H9A119.4
S2—Pd1—S2i180.0N3—C10—C11112.4 (3)
C2—S1—Pd1102.19 (11)N3—C10—H10A109.1
C3—S2—Pd1102.16 (11)C11—C10—H10A109.1
C9—N3—C5119.4 (3)N3—C10—H10B109.1
C9—N3—C10119.7 (3)C11—C10—H10B109.1
C5—N3—C10120.9 (3)H10A—C10—H10B107.9
N1—C1—C2176.6 (4)C12—C11—C16117.5 (3)
C3—C2—C1121.8 (3)C12—C11—C10121.4 (3)
C3—C2—S1122.8 (3)C16—C11—C10121.1 (3)
C1—C2—S1115.3 (2)F1—C12—C11117.9 (3)
C2—C3—C4120.8 (3)F1—C12—C13118.2 (3)
C2—C3—S2122.8 (2)C11—C12—C13123.9 (3)
C4—C3—S2116.3 (3)C12—C13—C14117.0 (3)
N2—C4—C3177.6 (4)C12—C13—H13A121.5
N3—C5—C6121.0 (3)C14—C13—H13A121.5
N3—C5—H5A119.5C15—C14—C13121.5 (3)
C6—C5—H5A119.5C15—C14—Br1119.0 (3)
C5—C6—C7119.9 (3)C13—C14—Br1119.5 (3)
C5—C6—H6A120.0C14—C15—C16119.4 (3)
C7—C6—H6A120.0C14—C15—H15A120.3
C8—C7—C6119.0 (3)C16—C15—H15A120.3
C8—C7—H7A120.5C11—C16—C15120.8 (3)
C6—C7—H7A120.5C11—C16—H16A119.6
C7—C8—C9119.4 (3)C15—C16—H16A119.6
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6A···F1ii0.932.403.079 (4)130
Symmetry code: (ii) x+2, y+1, z+2.

Experimental details

Crystal data
Chemical formula(C12H10BrFN)2[Pd(C4N2S2)2]
Mr921.00
Crystal system, space groupTriclinic, 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)
V3)835.5 (4)
Z1
Radiation typeMo Kα
µ (mm1)3.24
Crystal size (mm)0.15 × 0.10 × 0.10
Data collection
DiffractometerSiemens CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(North et al., 1984)
Tmin, Tmax0.665, 0.728
No. of measured, independent and
observed [I > 2σ(I)] reflections
4372, 2907, 2348
Rint0.016
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.065, 1.12
No. of reflections2907
No. of parameters214
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.37, 0.47

Computer programs: SMART (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.

Selected geometric parameters (Å, º) top
Pd1—S12.2872 (11)Pd1—S22.2941 (10)
S1—Pd1—S289.56 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6A···F1i0.932.403.079 (4)130
Symmetry code: (i) x+2, y+1, z+2.
 

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