supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m2167    [ doi:10.1107/S1600536807033284 ]

Poly[[bis(18-crown-6)bis([mu]3-1,1-dicyanoethylene-2,2-dithiolato)dipotassium(I)nickelate(II)] 1,2-dichloroethane solvate]

S.-Z. Fu, D.-Q. Wang and J.-M. Dou

Abstract top

The title complex, [K2Ni(C4N2S2)2(C12H24O6)2]·C2H4Cl2, consists of two symmetry-equivalent [K(18C6)]+ complex cations (18C6 = 18-crown-6), one centrosymmetric [Ni(i-mnt)2]2- complex anion (i-mnt = 1,1-dicyanoethylene-2,2-dithiolate), and a ClCH2CH2Cl solvent molecule that also lies on an inversion center. The [K(18C6)]+ cations and [Ni(i-mnt)2]2- complex anions form a two-dimensional network through K...N interactions.

Comment top

In recent years, metal coordination complexes with one-dimensional polymeric structures have attracted interest owing to their important applications as materials with unusual properties (Chen &Suslick, 1993). The complexes formed by crown ethers, alkali metal cations, and transition metal bis(dithiolate) anions, in which the bis(dithiolate) ligands include i-mnt (Long et al., 1998) have attracted widespread interest due to their unusual crystal structures and nusual electrical, magnetic and optical properties (Nakamura et al., 1998). The title complex consists of two [K(18 C6)]+ complex cations, one centrosymmetric [Ni(i-mnt)2]2- complex anion, and a solvent molecule. The Ni atom is located on an inversion center and does not bond directly to the O atoms of the crown ether. It is coordinated by four S atoms from two i-mnt ligands. The NiS4 group is square planar. In the complex cation [K(18 C6)]+, the potassium ion lies within the crown ether cavity, 0.2038Å out of the plane formed by the six ether oxygen atoms. The K+ ion is also coordinated by two N atoms from i-mnt ligands of different [Ni(i-mnt)2]2- complex anions. Thus the [K(18 C6)]+ cations and [Ni(i-mnt)2]2- complex anions form a two-dimensional network bridged by K—N interactions. The solvent molecule also lies on an inversion center.

Related literature top

For related literature, see: Chen & Suslick (1993); Long et al. (1998); Nakamura et al. (1998).

Experimental top

To a solution of 18-crown-6 (2.0 mmol) in 1,2-dichloroethane (10.0 ml) was added 5 ml of 1,2-dichloroethane containing NiCl2 (0.5 mmol) and K2(i-mnt) (1 mmol). The reaction mixture was stirred for 2 h at room temperature and then filtered. The precipitate was dissolved in 4:1 diethyl ether/1,2-dichloroethane. Colorless single crystals were obtained by slowly evaporating the solution. Elemental analysis found: H 5.02, C 39.08, N 5.36%; calculated for C34H52Cl2K2N4O12S4Ni: H 5.23, C 38.93, N 5.12%.

Refinement top

All H atoms were positioned geometrically and treated as riding on their parent atoms, with 0.97Å and the Uiso(H) values were set at 1.2Ueq(C) for C-bound H atoms..

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A segment of the polymeric structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms and the solvent molecule have been omitted for clarity. [Symmetry code for unlabeled atoms: 1 - x, 1 - y, 1 - z.]
[Figure 2] Fig. 2. Crystal packing of the title complex. H atoms and solvent molecules have been omitted.
[Figure 3] Fig. 3. Two-dimensional sheet network of the title complex. H atoms and solvent molecules have been omitted.
Poly[[bis(18-crown-6)bis(µ3-1,1-dicyanoethylene-2,2-\ dithiolato)dipotassium(I)nickelate(II)] 1,2-dichloroethane solvate] top
Crystal data top
[K2Ni(C4N2S2)2(C12H24O6)2]·C2H4Cl2F(000) = 1088
Mr = 1044.85Dx = 1.446 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2404 reflections
a = 8.271 (1) Åθ = 2.4–20.9°
b = 13.067 (2) ŵ = 0.92 mm−1
c = 22.207 (2) ÅT = 298 K
β = 90.140 (2)°Block, colourless
V = 2400.1 (5) Å30.40 × 0.32 × 0.31 mm
Z = 2
Data collection top
Siemens SMART CCD
diffractometer		4882 independent reflections
Radiation source: fine-focus sealed tube2717 reflections with I > 2σ(I)
graphiteRint = 0.041
φ and ω scansθmax = 26.4°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→10
Tmin = 0.710, Tmax = 0.763k = −11→16
13861 measured reflectionsl = −27→26
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0507P)2]
where P = (Fo2 + 2Fc2)/3
4882 reflections(Δ/σ)max < 0.001
262 parametersΔρmax = 0.59 e Å−3
3 restraintsΔρmin = −0.77 e Å−3
Crystal data top
[K2Ni(C4N2S2)2(C12H24O6)2]·C2H4Cl2V = 2400.1 (5) Å3
Mr = 1044.85Z = 2
Monoclinic, P21/cMo Kα radiation
a = 8.271 (1) ŵ = 0.92 mm−1
b = 13.067 (2) ÅT = 298 K
c = 22.207 (2) Å0.40 × 0.32 × 0.31 mm
β = 90.140 (2)°
Data collection top
Siemens SMART CCD
diffractometer		4882 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2717 reflections with I > 2σ(I)
Tmin = 0.710, Tmax = 0.763Rint = 0.041
13861 measured reflectionsθmax = 26.4°
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.128Δρmax = 0.59 e Å−3
S = 1.01Δρmin = −0.77 e Å−3
4882 reflectionsAbsolute structure: ?
262 parametersFlack parameter: ?
3 restraintsRogers parameter: ?
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
Ni10.50000.50000.50000.0446 (2)
K1−0.04263 (11)0.51950 (6)0.17024 (4)0.0524 (2)
Cl10.11657 (19)0.41379 (12)0.56953 (7)0.1072 (5)
N10.1579 (4)0.6009 (2)0.27356 (14)0.0524 (2)
N20.2288 (5)0.8652 (3)0.39120 (16)0.0765 (12)
O1−0.2843 (4)0.4976 (2)0.25695 (13)0.0724 (9)
O2−0.3427 (4)0.6163 (2)0.15473 (14)0.0680 (8)
O3−0.0790 (4)0.6762 (2)0.08341 (13)0.0680 (8)
O40.1728 (4)0.5284 (2)0.07367 (12)0.0675 (8)
O50.2242 (3)0.3857 (2)0.16313 (12)0.0603 (8)
O6−0.0334 (4)0.3540 (2)0.24499 (12)0.0645 (8)
S10.38775 (13)0.48585 (7)0.40962 (4)0.0531 (3)
S20.43037 (13)0.66007 (7)0.48093 (4)0.0513 (3)
C1−0.4432 (6)0.5184 (4)0.2352 (2)0.0839 (15)
H1A−0.51840.51910.26870.101*
H1B−0.47630.46480.20760.101*
C2−0.4478 (6)0.6182 (4)0.2041 (2)0.0783 (14)
H2A−0.55700.63240.19050.094*
H2B−0.41550.67200.23180.094*
C3−0.3468 (6)0.7057 (4)0.1196 (2)0.0769 (14)
H3A−0.30950.76360.14320.092*
H3B−0.45680.71940.10660.092*
C4−0.2412 (6)0.6917 (4)0.0663 (2)0.0791 (14)
H4A−0.27850.63320.04320.095*
H4B−0.24840.75170.04080.095*
C50.0254 (6)0.6647 (4)0.0331 (2)0.0811 (15)
H5A0.03600.72980.01250.097*
H5B−0.02120.61590.00500.097*
C60.1863 (6)0.6287 (4)0.0522 (2)0.0791 (14)
H6A0.26040.63080.01850.095*
H6B0.22820.67290.08370.095*
C70.3235 (5)0.4777 (4)0.08011 (19)0.0680 (13)
H7A0.39390.51610.10680.082*
H7B0.37610.47140.04130.082*
C80.2907 (6)0.3754 (4)0.10550 (19)0.0698 (13)
H8A0.21600.33880.07960.084*
H8B0.39040.33650.10780.084*
C90.1869 (6)0.2907 (3)0.1902 (2)0.0770 (14)
H9A0.28360.24900.19310.092*
H9B0.10820.25430.16580.092*
C100.1208 (6)0.3092 (4)0.2507 (2)0.0745 (14)
H10A0.11280.24510.27250.089*
H10B0.19200.35450.27300.089*
C11−0.1054 (6)0.3763 (4)0.3006 (2)0.0877 (16)
H11A−0.04900.43260.31990.105*
H11B−0.09950.31710.32680.105*
C12−0.2778 (6)0.4047 (4)0.2898 (2)0.0923 (17)
H12A−0.33150.35080.26730.111*
H12B−0.33310.41270.32800.111*
C130.3545 (4)0.6152 (3)0.41369 (15)0.0440 (9)
C140.2763 (4)0.6752 (2)0.37046 (14)0.0455 (9)
C150.2118 (5)0.6326 (3)0.31712 (16)0.0532 (10)
C160.2502 (5)0.7801 (3)0.38195 (16)0.0514 (10)
C170.0361 (7)0.5200 (4)0.5271 (2)0.1024 (19)
H17A−0.04430.55600.55070.123*
H17B0.12200.56760.51710.123*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0458 (4)0.0411 (4)0.0470 (4)0.0044 (3)−0.0006 (3)−0.0004 (3)
K10.0550 (6)0.0498 (5)0.0525 (5)0.0015 (4)−0.0030 (4)0.0027 (4)
Cl10.0982 (12)0.1102 (12)0.1131 (11)0.0054 (9)0.0116 (9)0.0209 (9)
N10.0550 (6)0.0498 (5)0.0525 (5)0.0015 (4)−0.0030 (4)0.0027 (4)
N20.109 (3)0.051 (2)0.070 (2)0.015 (2)−0.027 (2)0.001 (2)
O10.060 (2)0.098 (3)0.0594 (18)−0.0012 (18)0.0029 (15)0.0034 (17)
O20.067 (2)0.063 (2)0.074 (2)0.0108 (16)−0.0034 (17)−0.0042 (17)
O30.076 (2)0.066 (2)0.0623 (19)−0.0012 (16)−0.0194 (17)0.0096 (15)
O40.063 (2)0.073 (2)0.0662 (19)−0.0087 (16)0.0000 (15)0.0185 (16)
O50.064 (2)0.0621 (19)0.0545 (17)0.0056 (15)−0.0014 (15)−0.0014 (15)
O60.068 (2)0.071 (2)0.0554 (18)0.0044 (16)−0.0046 (16)0.0133 (15)
S10.0644 (7)0.0423 (6)0.0527 (6)0.0048 (5)−0.0033 (5)−0.0047 (5)
S20.0583 (7)0.0412 (6)0.0543 (6)0.0033 (5)−0.0100 (5)−0.0044 (5)
C10.055 (3)0.124 (5)0.072 (3)0.002 (3)0.006 (3)−0.003 (3)
C20.058 (3)0.100 (4)0.077 (3)0.013 (3)−0.011 (3)−0.022 (3)
C30.079 (4)0.066 (3)0.086 (3)0.015 (3)−0.033 (3)−0.006 (3)
C40.089 (4)0.070 (3)0.079 (3)0.000 (3)−0.028 (3)0.013 (3)
C50.111 (5)0.066 (3)0.067 (3)−0.004 (3)−0.011 (3)0.023 (3)
C60.083 (4)0.083 (4)0.071 (3)−0.020 (3)−0.003 (3)0.020 (3)
C70.051 (3)0.094 (4)0.059 (3)−0.006 (3)0.000 (2)−0.006 (3)
C80.062 (3)0.080 (4)0.067 (3)0.008 (3)−0.003 (2)−0.010 (3)
C90.077 (4)0.061 (3)0.093 (4)0.021 (3)−0.012 (3)0.012 (3)
C100.080 (4)0.073 (3)0.071 (3)0.008 (3)−0.017 (3)0.026 (3)
C110.099 (4)0.111 (4)0.054 (3)0.004 (3)0.003 (3)0.026 (3)
C120.080 (4)0.125 (5)0.072 (3)−0.004 (4)0.023 (3)0.025 (3)
C130.040 (2)0.042 (2)0.050 (2)−0.0022 (17)0.0091 (18)−0.0034 (18)
C140.045 (2)0.044 (2)0.048 (2)0.0009 (18)−0.0013 (19)−0.0036 (18)
C150.052 (3)0.054 (3)0.053 (2)0.005 (2)−0.006 (2)−0.005 (2)
C160.056 (3)0.054 (3)0.044 (2)0.002 (2)−0.009 (2)0.007 (2)
C170.070 (4)0.113 (5)0.125 (5)−0.026 (3)0.035 (4)−0.025 (4)
Geometric parameters (Å, °) top
Ni1—S2i2.2101 (10)C2—H2A0.970
Ni1—S22.2101 (10)C2—H2B0.970
Ni1—S12.2170 (10)C3—C41.483 (6)
Ni1—S1i2.2170 (10)C3—H3A0.970
K1—O62.727 (3)C3—H3B0.970
K1—O12.793 (3)C4—H4A0.970
K1—O42.794 (3)C4—H4B0.970
K1—O22.806 (3)C5—C61.473 (6)
K1—O52.820 (3)C5—H5A0.970
K1—O32.828 (3)C5—H5B0.970
K1—N2ii2.879 (4)C6—H6A0.970
K1—N13.021 (3)C6—H6B0.970
Cl1—C171.803 (7)C7—C81.476 (6)
N1—C151.142 (4)C7—H7A0.970
N2—C161.145 (5)C7—H7B0.970
N2—K1iii2.879 (4)C8—H8A0.970
O1—C121.417 (5)C8—H8B0.970
O1—C11.426 (5)C9—C101.471 (6)
O2—C21.402 (5)C9—H9A0.970
O2—C31.406 (5)C9—H9B0.970
O3—C41.408 (5)C10—H10A0.970
O3—C51.422 (5)C10—H10B0.970
O4—C61.399 (5)C11—C121.492 (6)
O4—C71.418 (5)C11—H11A0.970
O5—C81.401 (4)C11—H11B0.970
O5—C91.413 (5)C12—H12A0.970
O6—C111.403 (5)C12—H12B0.970
O6—C101.409 (5)C13—C141.397 (3)
S1—C131.715 (4)C14—C161.411 (4)
S2—C131.721 (4)C14—C151.412 (3)
C1—C21.475 (6)C17—C17iv1.440 (10)
C1—H1A0.970C17—H17A0.970
C1—H1B0.970C17—H17B0.970
S2i—Ni1—S2180O2—C3—H3B109.9
S2i—Ni1—S1101.71 (4)C4—C3—H3B109.9
S2—Ni1—S178.29 (4)H3A—C3—H3B108.3
S2i—Ni1—S1i78.29 (4)O3—C4—C3111.4 (4)
S2—Ni1—S1i101.71 (4)O3—C4—H4A109.3
S1—Ni1—S1i180C3—C4—H4A109.3
O6—K1—O161.19 (9)O3—C4—H4B109.3
O6—K1—O4118.91 (9)C3—C4—H4B109.3
O1—K1—O4172.78 (9)H4A—C4—H4B108.0
O6—K1—O2117.09 (10)O3—C5—C6110.9 (4)
O1—K1—O259.78 (9)O3—C5—H5A109.5
O4—K1—O2116.91 (9)C6—C5—H5A109.5
O6—K1—O561.43 (9)O3—C5—H5B109.5
O1—K1—O5122.43 (9)C6—C5—H5B109.5
O4—K1—O558.82 (8)H5A—C5—H5B108.1
O2—K1—O5164.70 (9)O4—C6—C5108.9 (4)
O6—K1—O3172.71 (9)O4—C6—H6A109.9
O1—K1—O3117.98 (10)C5—C6—H6A109.9
O4—K1—O360.89 (9)O4—C6—H6B109.9
O2—K1—O359.83 (9)C5—C6—H6B109.9
O5—K1—O3119.51 (9)H6A—C6—H6B108.3
O6—K1—N2ii75.36 (10)O4—C7—C8107.4 (4)
O1—K1—N2ii82.66 (10)O4—C7—H7A110.2
O4—K1—N2ii90.38 (10)C8—C7—H7A110.2
O2—K1—N2ii77.62 (11)O4—C7—H7B110.2
O5—K1—N2ii87.53 (10)C8—C7—H7B110.2
O3—K1—N2ii97.37 (10)H7A—C7—H7B108.5
O6—K1—N178.60 (9)O5—C8—C7109.6 (4)
O1—K1—N184.54 (9)O5—C8—H8A109.8
O4—K1—N1102.62 (9)C7—C8—H8A109.8
O2—K1—N1114.72 (9)O5—C8—H8B109.8
O5—K1—N180.37 (8)C7—C8—H8B109.8
O3—K1—N1108.67 (9)H8A—C8—H8B108.2
N2ii—K1—N1153.96 (10)O5—C9—C10109.0 (4)
C15—N1—K1169.6 (3)O5—C9—H9A109.9
C16—N2—K1iii132.7 (3)C10—C9—H9A109.9
C12—O1—C1111.8 (4)O5—C9—H9B109.9
C12—O1—K1114.6 (3)C10—C9—H9B109.9
C1—O1—K1114.1 (2)H9A—C9—H9B108.3
C2—O2—C3114.0 (4)O6—C10—C9108.9 (4)
C2—O2—K1117.5 (3)O6—C10—H10A109.9
C3—O2—K1117.6 (3)C9—C10—H10A109.9
C4—O3—C5112.5 (3)O6—C10—H10B109.9
C4—O3—K1112.8 (3)C9—C10—H10B109.9
C5—O3—K1113.3 (2)H10A—C10—H10B108.3
C6—O4—C7113.7 (3)O6—C11—C12108.5 (4)
C6—O4—K1110.6 (3)O6—C11—H11A110.0
C7—O4—K1117.7 (2)C12—C11—H11A110.0
C8—O5—C9113.0 (3)O6—C11—H11B110.0
C8—O5—K1114.8 (2)C12—C11—H11B110.0
C9—O5—K1110.4 (2)H11A—C11—H11B108.4
C11—O6—C10113.2 (3)O1—C12—C11109.3 (4)
C11—O6—K1111.1 (3)O1—C12—H12A109.8
C10—O6—K1114.1 (2)C11—C12—H12A109.8
C13—S1—Ni186.39 (12)O1—C12—H12B109.8
C13—S2—Ni186.45 (12)C11—C12—H12B109.8
O1—C1—C2110.4 (4)H12A—C12—H12B108.3
O1—C1—H1A109.6C14—C13—S1126.2 (3)
C2—C1—H1A109.6C14—C13—S2124.9 (3)
O1—C1—H1B109.6S1—C13—S2108.9 (2)
C2—C1—H1B109.6C13—C14—C16119.4 (3)
H1A—C1—H1B108.1C13—C14—C15121.9 (3)
O2—C2—C1109.6 (4)C16—C14—C15118.5 (3)
O2—C2—H2A109.7N1—C15—C14178.0 (4)
C1—C2—H2A109.7N2—C16—C14179.9 (5)
O2—C2—H2B109.7C17iv—C17—Cl1108.1 (6)
C1—C2—H2B109.7C17iv—C17—H17A110.1
H2A—C2—H2B108.2Cl1—C17—H17A110.1
O2—C3—C4109.1 (4)C17iv—C17—H17B110.1
O2—C3—H3A109.9Cl1—C17—H17B110.1
C4—C3—H3A109.9H17A—C17—H17B108.4
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y−1/2, −z+1/2; (iii) −x, y+1/2, −z+1/2; (iv) −x, −y+1, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Ni1—S22.2101 (10)K1—O22.806 (3)
Ni1—S12.2170 (10)K1—O32.828 (3)
K1—O62.727 (3)K1—N2i2.879 (4)
K1—O12.793 (3)K1—N13.021 (3)
K1—O42.794 (3)
S2—Ni1—S178.29 (4)
Symmetry codes: (i) −x, y−1/2, −z+1/2.
Acknowledgements top

We acknowledge financial support from the Shandong Province Science Foundation and the State Key Laboratory of Crystalline Materials, Shandong University, People's Republic of China.

references
References top

Chen, C. T. & Suslick, K. S. (1993). Coord. Chem. 128, 293–299.

Long, D. L., Cui, Y., Chen, J. T., Cheng, W. D. & Huang, J. S. (1998). Polyhedron, 17, 3969–3974.

Nakamura, T., Akutagawa, T., Honda, K., Underhill, A. E., Coomber, A. T. & Friend, R. H. (1998). Nature (London), 394, 159–172.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Sheldrick, G. M. (1997b). SHELXTL Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Systems Inc., Madison, Wisconsin, USA.