Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807020028/sj2302sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807020028/sj2302Isup2.hkl |
CCDC reference: 209413
To a solution of 18-crown-6 (2.0 mmol) in 1,2-dichloroethane (10.0 ml) was added 5 ml 1,2-dichloroethane mixture of CuCl2 (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 (v/v) diethyl ether/ 1,2-dichloroethane and colorless single crystals were obtained by slowly evaporating this solution. Elemental analysis found: H 4.99, C 38.90, N 5.34%; calculated for C34H52Cl2K2N4O12S4Cu: H 4.87, C 38.95, N 5.22%.
All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.97 Å, Uiso = 1.2Ueq (C) for the CH2 atoms.
In recent years, metal coordination complexes with polymeric structures have attracted interest owing to their important applications as materials with unusual properties (Chen et al., 1993). The complexes formed by crown ether cations and transition metal bis(dithiolate) salts, including 1,1-dicyanoethylene-2,2dithiolate (i-mnt2-) (Long et al., 1998) have attracted widespread interest due to their novel structures and unusual electrical, magnetic and optical properties (Nakamura et al., 1998). We report here one such novel complex [K(18Crown-6)]2[Cu(i-mnt)2], Fig. 1.
In the title complex, the CuII atom lies on an inversion centre while the 1,2-dichloroethane solvate lies about an inversion centre. The asymmetric unit therefore comprises one [K(18Crown-6)]+ cation, one half of the [Cu(i-mnt)2]2- anion (i-mnt = 1,1-dicyanoethylene-2,2dithiolate) and one half of the dichloroethane solvate. In the cation [K(18Crown-6)]+, the potassium ion lies within the crown ether cage with K—O bond lengths in the range 2.722 (5) to 2.826 (5) Å. The K+ ion lies 0.2210Å out of meanplane through the six ether O atoms. Each K+ ion also binds in a trans configuration to two N atoms from adjacent i-mnt ligands with K—N distances 2.828 (7) and 2.963 (7) Å. The Cu atoms adopt a distorted square planar coordination geometry with Cu—S distances 2.302 (2) and 2.3324 (19) Å. In the crystal structure, K—N bonds from each of the four cyano- groups link the cations and anions into planar sheets along the diagonal of the ac plane, Fig 2, and these sheets pack in layers in the bc plane, Fig. 3.
For applications of coordination polymers, see: Chen & Suslick (1993); for the structures and applications of crown ether transition metal bis(dithiolate) salts, see: Long et al. (1998) and Nakamura et al. (1998).
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.
[CuK2(C4N2S2)2(C12H24O6)2]·C2H4Cl2 | F(000) = 1090 |
Mr = 1049.68 | Dx = 1.451 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1005 reflections |
a = 8.259 (3) Å | θ = 2.4–18° |
b = 13.084 (4) Å | µ = 0.97 mm−1 |
c = 22.228 (7) Å | T = 293 K |
β = 90.413 (6)° | Block, colourless |
V = 2401.8 (13) Å3 | 0.22 × 0.15 × 0.07 mm |
Z = 2 |
Siemens SMART CCD area-detector diffractometer | 4281 independent reflections |
Radiation source: fine-focus sealed tube | 1698 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.084 |
φ and ω scans | θmax = 25.1°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −9→9 |
Tmin = 0.815, Tmax = 0.935 | k = −11→15 |
12535 measured reflections | l = −23→26 |
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.171 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.051P)2] where P = (Fo2 + 2Fc2)/3 |
4281 reflections | (Δ/σ)max < 0.001 |
268 parameters | Δρmax = 0.51 e Å−3 |
0 restraints | Δρmin = −0.44 e Å−3 |
[CuK2(C4N2S2)2(C12H24O6)2]·C2H4Cl2 | V = 2401.8 (13) Å3 |
Mr = 1049.68 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.259 (3) Å | µ = 0.97 mm−1 |
b = 13.084 (4) Å | T = 293 K |
c = 22.228 (7) Å | 0.22 × 0.15 × 0.07 mm |
β = 90.413 (6)° |
Siemens SMART CCD area-detector diffractometer | 4281 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1698 reflections with I > 2σ(I) |
Tmin = 0.815, Tmax = 0.935 | Rint = 0.084 |
12535 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.171 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.51 e Å−3 |
4281 reflections | Δρmin = −0.44 e Å−3 |
268 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 | ||
Cu1 | 0.5000 | 0.5000 | 0.5000 | 0.0482 (4) | |
K1 | −0.0443 (2) | 0.47985 (13) | 0.82898 (7) | 0.0514 (5) | |
Cl1 | 0.1390 (3) | 0.5783 (2) | 0.43296 (12) | 0.1075 (10) | |
N1 | 0.1485 (8) | 0.3983 (5) | 0.7278 (3) | 0.070 (2) | |
N2 | 0.2218 (9) | 0.1339 (6) | 0.6114 (3) | 0.077 (2) | |
O1 | 0.1706 (7) | 0.4726 (5) | 0.9259 (2) | 0.0674 (16) | |
O2 | −0.0850 (7) | 0.3246 (4) | 0.9160 (2) | 0.0665 (16) | |
O3 | −0.3476 (7) | 0.3877 (4) | 0.8427 (3) | 0.0720 (18) | |
O4 | −0.2879 (6) | 0.5039 (5) | 0.7438 (2) | 0.0705 (16) | |
O5 | −0.0337 (7) | 0.6458 (4) | 0.7553 (2) | 0.0641 (16) | |
O6 | 0.2236 (6) | 0.6121 (4) | 0.8357 (2) | 0.0595 (15) | |
S1 | 0.3801 (2) | 0.51358 (15) | 0.59435 (8) | 0.0539 (6) | |
S2 | 0.4227 (2) | 0.33487 (15) | 0.52112 (9) | 0.0527 (6) | |
C1 | 0.1820 (11) | 0.3747 (8) | 0.9473 (4) | 0.080 (3) | |
H1A | 0.2572 | 0.3726 | 0.9810 | 0.096* | |
H1B | 0.2230 | 0.3301 | 0.9160 | 0.096* | |
C2 | 0.0208 (12) | 0.3385 (7) | 0.9668 (4) | 0.083 (3) | |
H2A | 0.0324 | 0.2743 | 0.9881 | 0.100* | |
H2B | −0.0261 | 0.3880 | 0.9941 | 0.100* | |
C3 | −0.2536 (12) | 0.3101 (7) | 0.9293 (4) | 0.097 (4) | |
H3A | −0.2917 | 0.3673 | 0.9530 | 0.116* | |
H3B | −0.2660 | 0.2486 | 0.9531 | 0.116* | |
C4 | −0.3541 (11) | 0.3014 (9) | 0.8742 (4) | 0.088 (3) | |
H4A | −0.3153 | 0.2451 | 0.8499 | 0.106* | |
H4B | −0.4654 | 0.2872 | 0.8851 | 0.106* | |
C5 | −0.4536 (11) | 0.3868 (8) | 0.7928 (4) | 0.083 (3) | |
H5A | −0.5629 | 0.3719 | 0.8058 | 0.100* | |
H5B | −0.4209 | 0.3344 | 0.7645 | 0.100* | |
C6 | −0.4481 (10) | 0.4870 (8) | 0.7642 (4) | 0.077 (3) | |
H6A | −0.5234 | 0.4894 | 0.7305 | 0.092* | |
H6B | −0.4783 | 0.5396 | 0.7927 | 0.092* | |
C7 | −0.2805 (11) | 0.5978 (9) | 0.7127 (4) | 0.090 (3) | |
H7A | −0.3321 | 0.6508 | 0.7363 | 0.108* | |
H7B | −0.3382 | 0.5921 | 0.6746 | 0.108* | |
C8 | −0.1091 (12) | 0.6258 (7) | 0.7016 (4) | 0.086 (3) | |
H8A | −0.0545 | 0.5700 | 0.6814 | 0.103* | |
H8B | −0.1044 | 0.6856 | 0.6759 | 0.103* | |
C9 | 0.1212 (11) | 0.6881 (7) | 0.7491 (4) | 0.070 (3) | |
H9A | 0.1141 | 0.7517 | 0.7268 | 0.084* | |
H9B | 0.1895 | 0.6414 | 0.7268 | 0.084* | |
C10 | 0.1904 (11) | 0.7066 (7) | 0.8072 (4) | 0.076 (3) | |
H10A | 0.2896 | 0.7456 | 0.8032 | 0.092* | |
H10B | 0.1156 | 0.7460 | 0.8313 | 0.092* | |
C11 | 0.2911 (10) | 0.6221 (7) | 0.8912 (4) | 0.070 (3) | |
H11A | 0.2189 | 0.6609 | 0.9167 | 0.085* | |
H11B | 0.3921 | 0.6596 | 0.8881 | 0.085* | |
C12 | 0.3222 (10) | 0.5218 (8) | 0.9184 (3) | 0.072 (3) | |
H12A | 0.3913 | 0.4813 | 0.8925 | 0.087* | |
H12B | 0.3761 | 0.5299 | 0.9570 | 0.087* | |
C13 | 0.3473 (8) | 0.3831 (5) | 0.5889 (3) | 0.0432 (19) | |
C14 | 0.2677 (8) | 0.3243 (6) | 0.6315 (3) | 0.0429 (19) | |
C15 | 0.2029 (9) | 0.3687 (6) | 0.6860 (4) | 0.048 (2) | |
C16 | 0.2446 (9) | 0.2183 (7) | 0.6194 (3) | 0.049 (2) | |
C17 | 0.0317 (12) | 0.4761 (9) | 0.4737 (4) | 0.125 (4) | |
H17A | −0.0552 | 0.4481 | 0.4491 | 0.150* | |
H17B | 0.1055 | 0.4213 | 0.4845 | 0.150* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0521 (9) | 0.0443 (9) | 0.0482 (8) | −0.0080 (7) | 0.0057 (6) | 0.0008 (7) |
K1 | 0.0541 (11) | 0.0500 (12) | 0.0502 (10) | 0.0015 (9) | 0.0052 (8) | 0.0039 (9) |
Cl1 | 0.092 (2) | 0.118 (3) | 0.113 (2) | −0.0143 (18) | −0.0027 (17) | 0.0193 (19) |
N1 | 0.080 (6) | 0.078 (6) | 0.052 (5) | −0.011 (4) | 0.022 (4) | −0.010 (4) |
N2 | 0.111 (6) | 0.049 (5) | 0.072 (5) | −0.016 (5) | 0.034 (4) | 0.000 (4) |
O1 | 0.072 (4) | 0.064 (4) | 0.067 (4) | 0.015 (3) | 0.001 (3) | 0.021 (3) |
O2 | 0.077 (4) | 0.063 (4) | 0.059 (4) | 0.007 (3) | 0.012 (3) | 0.009 (3) |
O3 | 0.080 (5) | 0.048 (4) | 0.088 (5) | −0.008 (4) | 0.013 (4) | 0.012 (4) |
O4 | 0.055 (4) | 0.096 (5) | 0.060 (4) | 0.003 (4) | 0.004 (3) | 0.010 (4) |
O5 | 0.065 (4) | 0.075 (4) | 0.052 (4) | −0.005 (3) | 0.002 (3) | 0.010 (3) |
O6 | 0.063 (4) | 0.071 (4) | 0.044 (3) | −0.004 (3) | 0.001 (3) | 0.000 (3) |
S1 | 0.0668 (14) | 0.0437 (13) | 0.0513 (12) | −0.0061 (11) | 0.0078 (10) | −0.0024 (11) |
S2 | 0.0616 (14) | 0.0426 (13) | 0.0542 (12) | −0.0051 (11) | 0.0134 (10) | −0.0045 (10) |
C1 | 0.076 (7) | 0.092 (8) | 0.072 (6) | 0.026 (6) | 0.003 (5) | 0.004 (6) |
C2 | 0.122 (9) | 0.054 (6) | 0.074 (7) | 0.016 (6) | 0.015 (7) | 0.028 (5) |
C3 | 0.098 (8) | 0.057 (7) | 0.136 (10) | 0.015 (6) | 0.081 (8) | 0.035 (7) |
C4 | 0.054 (6) | 0.125 (11) | 0.087 (8) | −0.008 (7) | 0.011 (6) | −0.045 (8) |
C5 | 0.061 (7) | 0.125 (10) | 0.063 (6) | −0.012 (6) | 0.000 (5) | −0.021 (6) |
C6 | 0.054 (6) | 0.116 (9) | 0.061 (6) | 0.010 (6) | −0.003 (4) | 0.012 (6) |
C7 | 0.069 (8) | 0.147 (11) | 0.053 (6) | −0.004 (7) | −0.015 (5) | 0.013 (6) |
C8 | 0.105 (9) | 0.095 (8) | 0.058 (6) | −0.001 (7) | 0.006 (6) | 0.028 (6) |
C9 | 0.072 (7) | 0.076 (7) | 0.063 (6) | 0.001 (6) | 0.002 (5) | 0.019 (5) |
C10 | 0.074 (7) | 0.058 (7) | 0.097 (8) | −0.019 (5) | 0.016 (6) | 0.016 (6) |
C11 | 0.058 (6) | 0.053 (6) | 0.101 (8) | −0.001 (5) | 0.025 (6) | −0.004 (6) |
C12 | 0.043 (6) | 0.116 (9) | 0.058 (5) | 0.005 (6) | −0.002 (4) | −0.019 (6) |
C13 | 0.036 (4) | 0.044 (5) | 0.050 (5) | 0.005 (4) | −0.001 (4) | −0.007 (4) |
C14 | 0.040 (5) | 0.038 (5) | 0.051 (5) | −0.006 (4) | 0.005 (4) | 0.010 (4) |
C15 | 0.049 (5) | 0.047 (5) | 0.046 (5) | −0.007 (4) | −0.002 (4) | 0.009 (4) |
C16 | 0.055 (5) | 0.055 (6) | 0.037 (5) | −0.008 (5) | 0.013 (4) | 0.009 (5) |
C17 | 0.074 (8) | 0.150 (13) | 0.151 (12) | 0.040 (7) | −0.040 (8) | −0.038 (9) |
Cu1—S2 | 2.302 (2) | C1—H1B | 0.9700 |
Cu1—S2i | 2.302 (2) | C2—H2A | 0.9700 |
Cu1—S1i | 2.3324 (19) | C2—H2B | 0.9700 |
Cu1—S1 | 2.3324 (19) | C3—C4 | 1.478 (11) |
K1—O5 | 2.722 (5) | C3—H3A | 0.9700 |
K1—O4 | 2.771 (6) | C3—H3B | 0.9700 |
K1—O1 | 2.783 (5) | C4—H4A | 0.9700 |
K1—O3 | 2.798 (6) | C4—H4B | 0.9700 |
K1—O6 | 2.812 (6) | C5—C6 | 1.459 (11) |
K1—O2 | 2.826 (5) | C5—H5A | 0.9700 |
K1—N2ii | 2.828 (7) | C5—H5B | 0.9700 |
K1—N1 | 2.963 (7) | C6—H6A | 0.9700 |
K1—C8 | 3.454 (8) | C6—H6B | 0.9700 |
K1—C1 | 3.497 (9) | C7—C8 | 1.485 (11) |
K1—C9 | 3.533 (9) | C7—H7A | 0.9700 |
Cl1—C17 | 1.846 (13) | C7—H7B | 0.9700 |
N1—C15 | 1.107 (8) | C8—H8A | 0.9700 |
N2—C16 | 1.134 (9) | C8—H8B | 0.9700 |
N2—K1iii | 2.828 (7) | C9—C10 | 1.429 (10) |
O1—C1 | 1.370 (9) | C9—H9A | 0.9700 |
O1—C12 | 1.419 (9) | C9—H9B | 0.9700 |
O2—C2 | 1.433 (9) | C10—H10A | 0.9700 |
O2—C3 | 1.438 (9) | C10—H10B | 0.9700 |
O3—C4 | 1.330 (11) | C11—C12 | 1.468 (10) |
O3—C5 | 1.407 (9) | C11—H11A | 0.9700 |
O4—C7 | 1.411 (10) | C11—H11B | 0.9700 |
O4—C6 | 1.419 (9) | C12—H12A | 0.9700 |
O5—C8 | 1.368 (9) | C12—H12B | 0.9700 |
O5—C9 | 1.401 (9) | C13—C14 | 1.390 (9) |
O6—C11 | 1.357 (9) | C14—C16 | 1.425 (10) |
O6—C10 | 1.415 (9) | C14—C15 | 1.448 (10) |
S1—C13 | 1.733 (7) | C17—C17iv | 1.430 (17) |
S2—C13 | 1.751 (7) | C17—H17A | 0.9700 |
C1—C2 | 1.481 (11) | C17—H17B | 0.9700 |
C1—H1A | 0.9700 | ||
S2—Cu1—S2i | 180.000 (1) | C2—C1—H1B | 109.7 |
S2—Cu1—S1i | 103.42 (7) | K1—C1—H1B | 83.4 |
S2i—Cu1—S1i | 76.58 (7) | H1A—C1—H1B | 108.2 |
S2—Cu1—S1 | 76.58 (7) | O2—C2—C1 | 110.8 (7) |
S2i—Cu1—S1 | 103.42 (7) | O2—C2—H2A | 109.5 |
S1i—Cu1—S1 | 180.000 (1) | C1—C2—H2A | 109.5 |
O5—K1—O4 | 61.60 (18) | O2—C2—H2B | 109.5 |
O5—K1—O1 | 118.01 (19) | C1—C2—H2B | 109.5 |
O4—K1—O1 | 171.42 (17) | H2A—C2—H2B | 108.1 |
O5—K1—O3 | 116.23 (19) | O2—C3—C4 | 112.3 (7) |
O4—K1—O3 | 58.50 (18) | O2—C3—H3A | 109.2 |
O1—K1—O3 | 117.87 (19) | C4—C3—H3A | 109.2 |
O5—K1—O6 | 60.79 (17) | O2—C3—H3B | 109.2 |
O4—K1—O6 | 122.23 (18) | C4—C3—H3B | 109.2 |
O1—K1—O6 | 58.85 (17) | H3A—C3—H3B | 107.9 |
O3—K1—O6 | 164.57 (17) | O3—C4—C3 | 110.3 (9) |
O5—K1—O2 | 171.73 (16) | O3—C4—H4A | 109.6 |
O4—K1—O2 | 117.40 (19) | C3—C4—H4A | 109.6 |
O1—K1—O2 | 61.59 (18) | O3—C4—H4B | 109.6 |
O3—K1—O2 | 60.33 (18) | C3—C4—H4B | 109.6 |
O6—K1—O2 | 120.23 (18) | H4A—C4—H4B | 108.1 |
O5—K1—N2ii | 74.48 (18) | O3—C5—C6 | 108.4 (8) |
O4—K1—N2ii | 82.2 (2) | O3—C5—H5A | 110.0 |
O1—K1—N2ii | 89.5 (2) | C6—C5—H5A | 110.0 |
O3—K1—N2ii | 77.8 (2) | O3—C5—H5B | 110.0 |
O6—K1—N2ii | 87.0 (2) | C6—C5—H5B | 110.0 |
O2—K1—N2ii | 97.27 (18) | H5A—C5—H5B | 108.4 |
O5—K1—N1 | 79.11 (18) | O4—C6—C5 | 108.1 (7) |
O4—K1—N1 | 85.06 (18) | O4—C6—H6A | 110.1 |
O1—K1—N1 | 103.39 (18) | C5—C6—H6A | 110.1 |
O3—K1—N1 | 114.45 (19) | O4—C6—H6B | 110.1 |
O6—K1—N1 | 80.48 (17) | C5—C6—H6B | 110.1 |
O2—K1—N1 | 109.13 (18) | H6A—C6—H6B | 108.4 |
N2ii—K1—N1 | 153.6 (2) | O4—C7—C8 | 109.9 (8) |
O5—K1—C8 | 21.73 (18) | O4—C7—H7A | 109.7 |
O4—K1—C8 | 43.1 (2) | C8—C7—H7A | 109.7 |
O1—K1—C8 | 138.4 (2) | O4—C7—H7B | 109.7 |
O3—K1—C8 | 101.2 (2) | C8—C7—H7B | 109.7 |
O6—K1—C8 | 79.6 (2) | H7A—C7—H7B | 108.2 |
O2—K1—C8 | 160.0 (2) | O5—C8—C7 | 109.3 (7) |
N2ii—K1—C8 | 85.0 (2) | O5—C8—K1 | 47.4 (4) |
N1—K1—C8 | 70.0 (2) | C7—C8—K1 | 82.5 (5) |
O5—K1—C1 | 138.3 (2) | O5—C8—H8A | 109.8 |
O4—K1—C1 | 160.1 (2) | C7—C8—H8A | 109.8 |
O1—K1—C1 | 21.59 (18) | K1—C8—H8A | 84.0 |
O3—K1—C1 | 102.9 (2) | O5—C8—H8B | 109.8 |
O6—K1—C1 | 77.7 (2) | C7—C8—H8B | 109.8 |
O2—K1—C1 | 43.0 (2) | K1—C8—H8B | 157.3 |
N2ii—K1—C1 | 101.8 (2) | H8A—C8—H8B | 108.3 |
N1—K1—C1 | 98.1 (2) | O5—C9—C10 | 109.7 (7) |
C8—K1—C1 | 155.9 (2) | C10—C9—K1 | 80.2 (5) |
O5—K1—C9 | 21.24 (16) | O5—C9—H9A | 109.7 |
O4—K1—C9 | 81.4 (2) | C10—C9—H9A | 109.7 |
O1—K1—C9 | 99.7 (2) | K1—C9—H9A | 153.7 |
O3—K1—C9 | 137.5 (2) | O5—C9—H9B | 109.7 |
O6—K1—C9 | 40.96 (18) | C10—C9—H9B | 109.7 |
O2—K1—C9 | 161.2 (2) | K1—C9—H9B | 90.0 |
N2ii—K1—C9 | 83.7 (2) | H9A—C9—H9B | 108.2 |
N1—K1—C9 | 71.6 (2) | O6—C10—C9 | 109.4 (8) |
C8—K1—C9 | 38.7 (2) | O6—C10—H10A | 109.8 |
C1—K1—C9 | 118.3 (2) | C9—C10—H10A | 109.8 |
C15—N1—K1 | 171.1 (7) | O6—C10—H10B | 109.8 |
C16—N2—K1iii | 134.9 (6) | C9—C10—H10B | 109.8 |
C1—O1—C12 | 114.0 (7) | H10A—C10—H10B | 108.3 |
C1—O1—K1 | 110.0 (5) | O6—C11—C12 | 111.0 (7) |
C12—O1—K1 | 116.9 (4) | O6—C11—H11A | 109.4 |
C2—O2—C3 | 116.1 (7) | C12—C11—H11A | 109.4 |
C2—O2—K1 | 111.9 (5) | O6—C11—H11B | 109.4 |
C3—O2—K1 | 110.8 (5) | C12—C11—H11B | 109.4 |
C4—O3—C5 | 112.4 (8) | H11A—C11—H11B | 108.0 |
C4—O3—K1 | 117.6 (6) | O1—C12—C11 | 107.6 (7) |
C5—O3—K1 | 118.1 (5) | O1—C12—H12A | 110.2 |
C7—O4—C6 | 109.6 (7) | C11—C12—H12A | 110.2 |
C7—O4—K1 | 113.6 (5) | O1—C12—H12B | 110.2 |
C6—O4—K1 | 116.0 (4) | C11—C12—H12B | 110.2 |
C8—O5—C9 | 113.5 (7) | H12A—C12—H12B | 108.5 |
C8—O5—K1 | 110.8 (5) | C14—C13—S1 | 124.9 (5) |
C9—O5—K1 | 114.1 (5) | C14—C13—S2 | 124.0 (6) |
C11—O6—C10 | 113.6 (7) | S1—C13—S2 | 111.1 (4) |
C11—O6—K1 | 115.2 (5) | C13—C14—C16 | 118.2 (7) |
C10—O6—K1 | 111.3 (5) | C13—C14—C15 | 121.8 (7) |
C13—S1—Cu1 | 85.9 (2) | C16—C14—C15 | 119.9 (6) |
C13—S2—Cu1 | 86.4 (3) | N1—C15—C14 | 176.4 (9) |
O1—C1—C2 | 109.9 (7) | N2—C16—C14 | 177.4 (8) |
O1—C1—K1 | 48.4 (4) | C17iv—C17—Cl1 | 105.3 (12) |
C2—C1—K1 | 82.5 (5) | C17iv—C17—H17A | 110.7 |
O1—C1—H1A | 109.7 | Cl1—C17—H17A | 110.7 |
C2—C1—H1A | 109.7 | C17iv—C17—H17B | 110.7 |
K1—C1—H1A | 158.1 | Cl1—C17—H17B | 110.7 |
O1—C1—H1B | 109.7 | H17A—C17—H17B | 108.8 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y+1/2, −z+3/2; (iii) −x, y−1/2, −z+3/2; (iv) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [CuK2(C4N2S2)2(C12H24O6)2]·C2H4Cl2 |
Mr | 1049.68 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.259 (3), 13.084 (4), 22.228 (7) |
β (°) | 90.413 (6) |
V (Å3) | 2401.8 (13) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.97 |
Crystal size (mm) | 0.22 × 0.15 × 0.07 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.815, 0.935 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12535, 4281, 1698 |
Rint | 0.084 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.171, 1.00 |
No. of reflections | 4281 |
No. of parameters | 268 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.44 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL.
In recent years, metal coordination complexes with polymeric structures have attracted interest owing to their important applications as materials with unusual properties (Chen et al., 1993). The complexes formed by crown ether cations and transition metal bis(dithiolate) salts, including 1,1-dicyanoethylene-2,2dithiolate (i-mnt2-) (Long et al., 1998) have attracted widespread interest due to their novel structures and unusual electrical, magnetic and optical properties (Nakamura et al., 1998). We report here one such novel complex [K(18Crown-6)]2[Cu(i-mnt)2], Fig. 1.
In the title complex, the CuII atom lies on an inversion centre while the 1,2-dichloroethane solvate lies about an inversion centre. The asymmetric unit therefore comprises one [K(18Crown-6)]+ cation, one half of the [Cu(i-mnt)2]2- anion (i-mnt = 1,1-dicyanoethylene-2,2dithiolate) and one half of the dichloroethane solvate. In the cation [K(18Crown-6)]+, the potassium ion lies within the crown ether cage with K—O bond lengths in the range 2.722 (5) to 2.826 (5) Å. The K+ ion lies 0.2210Å out of meanplane through the six ether O atoms. Each K+ ion also binds in a trans configuration to two N atoms from adjacent i-mnt ligands with K—N distances 2.828 (7) and 2.963 (7) Å. The Cu atoms adopt a distorted square planar coordination geometry with Cu—S distances 2.302 (2) and 2.3324 (19) Å. In the crystal structure, K—N bonds from each of the four cyano- groups link the cations and anions into planar sheets along the diagonal of the ac plane, Fig 2, and these sheets pack in layers in the bc plane, Fig. 3.